US4451573A - Catalyst for polymerization of olefins - Google Patents
Catalyst for polymerization of olefins Download PDFInfo
- Publication number
- US4451573A US4451573A US06/385,221 US38522182A US4451573A US 4451573 A US4451573 A US 4451573A US 38522182 A US38522182 A US 38522182A US 4451573 A US4451573 A US 4451573A
- Authority
- US
- United States
- Prior art keywords
- sub
- compound
- catalyst
- component
- sup
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 title abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 44
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 39
- 150000001845 chromium compounds Chemical class 0.000 claims abstract description 31
- 239000011949 solid catalyst Substances 0.000 claims abstract description 30
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 27
- -1 amine compound Chemical class 0.000 claims abstract description 20
- 125000005843 halogen group Chemical group 0.000 claims abstract description 20
- 150000002291 germanium compounds Chemical class 0.000 claims abstract description 15
- 239000010936 titanium Substances 0.000 claims abstract description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 7
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 7
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical compound NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000003606 tin compounds Chemical class 0.000 claims abstract description 7
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 6
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 125000002734 organomagnesium group Chemical group 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 21
- 229940117975 chromium trioxide Drugs 0.000 claims description 21
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 claims description 21
- 239000011651 chromium Substances 0.000 claims description 19
- 150000002901 organomagnesium compounds Chemical class 0.000 claims description 16
- 229910052804 chromium Inorganic materials 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- 125000004429 atom Chemical group 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052790 beryllium Inorganic materials 0.000 claims description 4
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 150000002900 organolithium compounds Chemical class 0.000 claims description 4
- 125000003944 tolyl group Chemical group 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims 1
- 229940043774 zirconium oxide Drugs 0.000 claims 1
- 229910001928 zirconium oxide Inorganic materials 0.000 claims 1
- 150000002430 hydrocarbons Chemical group 0.000 abstract description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 32
- 239000005977 Ethylene Substances 0.000 description 32
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 30
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 19
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 17
- 239000007787 solid Substances 0.000 description 17
- 239000011777 magnesium Substances 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 125000000217 alkyl group Chemical group 0.000 description 15
- 239000004698 Polyethylene Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 10
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 description 5
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000012429 reaction media Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N Butanol Natural products CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 4
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- OJKANDGLELGDHV-UHFFFAOYSA-N disilver;dioxido(dioxo)chromium Chemical compound [Ag+].[Ag+].[O-][Cr]([O-])(=O)=O OJKANDGLELGDHV-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 150000004819 silanols Chemical class 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- QCOGKXLOEWLIDC-UHFFFAOYSA-N N-methylbutylamine Chemical compound CCCCNC QCOGKXLOEWLIDC-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- QWHNJUXXYKPLQM-UHFFFAOYSA-N dimethyl cyclopentane Natural products CC1(C)CCCC1 QWHNJUXXYKPLQM-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 2
- BFWMWWXRWVJXSE-UHFFFAOYSA-M fentin hydroxide Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(O)C1=CC=CC=C1 BFWMWWXRWVJXSE-UHFFFAOYSA-M 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N iso-butyl alcohol Natural products CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- QYAPHLRPFNSDNH-MRFRVZCGSA-N (4s,4as,5as,6s,12ar)-7-chloro-4-(dimethylamino)-1,6,10,11,12a-pentahydroxy-6-methyl-3,12-dioxo-4,4a,5,5a-tetrahydrotetracene-2-carboxamide;hydrochloride Chemical compound Cl.C1=CC(Cl)=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(=O)C(C(N)=O)=C(O)[C@@]4(O)C(=O)C3=C(O)C2=C1O QYAPHLRPFNSDNH-MRFRVZCGSA-N 0.000 description 1
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- CDULGHZNHURECF-UHFFFAOYSA-N 2,3-dimethylaniline 2,4-dimethylaniline 2,5-dimethylaniline 2,6-dimethylaniline 3,4-dimethylaniline 3,5-dimethylaniline Chemical group CC1=CC=C(N)C(C)=C1.CC1=CC=C(C)C(N)=C1.CC1=CC(C)=CC(N)=C1.CC1=CC=C(N)C=C1C.CC1=CC=CC(N)=C1C.CC1=CC=CC(C)=C1N CDULGHZNHURECF-UHFFFAOYSA-N 0.000 description 1
- VSYZXASVWVQEMR-UHFFFAOYSA-N 2-methylbuta-1,3-dienylalumane Chemical compound CC(=C[AlH2])C=C VSYZXASVWVQEMR-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UNJLOOOFZFOFRM-UHFFFAOYSA-N C(CCCCCCCCCCCC)[GeH3] Chemical compound C(CCCCCCCCCCCC)[GeH3] UNJLOOOFZFOFRM-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 101150108015 STR6 gene Proteins 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 1
- TUEIURIZJQRMQE-UHFFFAOYSA-N [2-(tert-butylsulfamoyl)phenyl]boronic acid Chemical compound CC(C)(C)NS(=O)(=O)C1=CC=CC=C1B(O)O TUEIURIZJQRMQE-UHFFFAOYSA-N 0.000 description 1
- FDXOHKDMDYSTDN-UHFFFAOYSA-N [Cr](=O)(=O)([O-])[O-].[Ge+2] Chemical class [Cr](=O)(=O)([O-])[O-].[Ge+2] FDXOHKDMDYSTDN-UHFFFAOYSA-N 0.000 description 1
- DOICJIFDQDPZHM-UHFFFAOYSA-K [OH-].C(CCCCCCCCCCCC)[Sn+3].[OH-].[OH-] Chemical compound [OH-].C(CCCCCCCCCCCC)[Sn+3].[OH-].[OH-] DOICJIFDQDPZHM-UHFFFAOYSA-K 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- JTCNNBSUKPHDMI-UHFFFAOYSA-N bromo(tributyl)germane Chemical compound CCCC[Ge](Br)(CCCC)CCCC JTCNNBSUKPHDMI-UHFFFAOYSA-N 0.000 description 1
- CNORLTIAZQYXAL-UHFFFAOYSA-N bromo(tridecyl)germane Chemical compound CCCCCCCCCCCCC[GeH2]Br CNORLTIAZQYXAL-UHFFFAOYSA-N 0.000 description 1
- VSKFNUKUWPSFJC-UHFFFAOYSA-M bromo(tridecyl)tin Chemical compound CCCCCCCCCCCCC[Sn]Br VSKFNUKUWPSFJC-UHFFFAOYSA-M 0.000 description 1
- BXPPRJFGNCDPFT-UHFFFAOYSA-N bromo(triethyl)germane Chemical compound CC[Ge](Br)(CC)CC BXPPRJFGNCDPFT-UHFFFAOYSA-N 0.000 description 1
- WMFCXPWEKRAKMH-UHFFFAOYSA-N bromo(trimethyl)germane Chemical compound C[Ge](C)(C)Br WMFCXPWEKRAKMH-UHFFFAOYSA-N 0.000 description 1
- RBXJUAXJPPYIMY-UHFFFAOYSA-N bromo(triphenyl)germane Chemical compound C=1C=CC=CC=1[Ge](C=1C=CC=CC=1)(Br)C1=CC=CC=C1 RBXJUAXJPPYIMY-UHFFFAOYSA-N 0.000 description 1
- FAMUPMBATZGWOV-UHFFFAOYSA-M bromo(triphenyl)stannane Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(Br)C1=CC=CC=C1 FAMUPMBATZGWOV-UHFFFAOYSA-M 0.000 description 1
- OCFLOWWNVUUZRC-UHFFFAOYSA-N bromo(tripropyl)germane Chemical compound CCC[Ge](Br)(CCC)CCC OCFLOWWNVUUZRC-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- BCFSVSISUGYRMF-UHFFFAOYSA-N calcium;dioxido(dioxo)chromium;dihydrate Chemical compound O.O.[Ca+2].[O-][Cr]([O-])(=O)=O BCFSVSISUGYRMF-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- YQHDNDJLMKPVBO-UHFFFAOYSA-N chloro(tridecyl)germane Chemical compound CCCCCCCCCCCCC[GeH2]Cl YQHDNDJLMKPVBO-UHFFFAOYSA-N 0.000 description 1
- SFZUASBCPOPDSH-UHFFFAOYSA-M chloro(tridecyl)tin Chemical compound CCCCCCCCCCCCC[Sn]Cl SFZUASBCPOPDSH-UHFFFAOYSA-M 0.000 description 1
- CZKMPDNXOGQMFW-UHFFFAOYSA-N chloro(triethyl)germane Chemical compound CC[Ge](Cl)(CC)CC CZKMPDNXOGQMFW-UHFFFAOYSA-N 0.000 description 1
- PIMYDFDXAUVLON-UHFFFAOYSA-M chloro(triethyl)stannane Chemical compound CC[Sn](Cl)(CC)CC PIMYDFDXAUVLON-UHFFFAOYSA-M 0.000 description 1
- ZZBNZZCHSNOXOH-UHFFFAOYSA-N chloro(trimethyl)germane Chemical compound C[Ge](C)(C)Cl ZZBNZZCHSNOXOH-UHFFFAOYSA-N 0.000 description 1
- KWTSZCJMWHGPOS-UHFFFAOYSA-M chloro(trimethyl)stannane Chemical compound C[Sn](C)(C)Cl KWTSZCJMWHGPOS-UHFFFAOYSA-M 0.000 description 1
- ONQMBYVVEVFYRP-UHFFFAOYSA-N chloro(triphenyl)germane Chemical compound C=1C=CC=CC=1[Ge](C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 ONQMBYVVEVFYRP-UHFFFAOYSA-N 0.000 description 1
- JCEGFAONHIYPBJ-UHFFFAOYSA-N chloro(tripropyl)germane Chemical compound CCC[Ge](Cl)(CCC)CCC JCEGFAONHIYPBJ-UHFFFAOYSA-N 0.000 description 1
- FVFLIQMADUVDSP-UHFFFAOYSA-M chloro(tripropyl)stannane Chemical compound CCC[Sn](Cl)(CCC)CCC FVFLIQMADUVDSP-UHFFFAOYSA-M 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- ANCLJVISBRWUTR-UHFFFAOYSA-N diaminophosphinic acid Chemical class NP(N)(O)=O ANCLJVISBRWUTR-UHFFFAOYSA-N 0.000 description 1
- VVYLMKNXUSVJAU-UHFFFAOYSA-N dianilinophosphinic acid Chemical compound C=1C=CC=CC=1NP(=O)(O)NC1=CC=CC=C1 VVYLMKNXUSVJAU-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- LAWOZCWGWDVVSG-UHFFFAOYSA-N dioctylamine Chemical compound CCCCCCCCNCCCCCCCC LAWOZCWGWDVVSG-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- NJVOZLGKTAPUTQ-UHFFFAOYSA-M fentin chloride Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 NJVOZLGKTAPUTQ-UHFFFAOYSA-M 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- IOANYFLVSWZRND-UHFFFAOYSA-N hydroxy(tripropyl)silane Chemical compound CCC[Si](O)(CCC)CCC IOANYFLVSWZRND-UHFFFAOYSA-N 0.000 description 1
- DUFWMVGFKLTJIF-UHFFFAOYSA-N iodo(tridecyl)germane Chemical compound CCCCCCCCCCCCC[GeH2]I DUFWMVGFKLTJIF-UHFFFAOYSA-N 0.000 description 1
- YXEJYHOYZZHRII-UHFFFAOYSA-M iodo(tridecyl)tin Chemical compound CCCCCCCCCCCCC[Sn]I YXEJYHOYZZHRII-UHFFFAOYSA-M 0.000 description 1
- KFLWSIOBXYVXBS-UHFFFAOYSA-N iodo(trimethyl)germane Chemical compound C[Ge](C)(C)I KFLWSIOBXYVXBS-UHFFFAOYSA-N 0.000 description 1
- JQNHPUJIZDXUTG-UHFFFAOYSA-N iodo(triphenyl)germane Chemical compound C=1C=CC=CC=1[Ge](C=1C=CC=CC=1)(I)C1=CC=CC=C1 JQNHPUJIZDXUTG-UHFFFAOYSA-N 0.000 description 1
- KJSACGHPPNXZFT-UHFFFAOYSA-M iodo(triphenyl)stannane Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(I)C1=CC=CC=C1 KJSACGHPPNXZFT-UHFFFAOYSA-M 0.000 description 1
- PIIZJDSIPQDKIR-UHFFFAOYSA-N iodo(tripropyl)germane Chemical compound CCC[Ge](I)(CCC)CCC PIIZJDSIPQDKIR-UHFFFAOYSA-N 0.000 description 1
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- CRGGPIWCSGOBDN-UHFFFAOYSA-N magnesium;dioxido(dioxo)chromium Chemical compound [Mg+2].[O-][Cr]([O-])(=O)=O CRGGPIWCSGOBDN-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- CLZGJKHEVKJLLS-UHFFFAOYSA-N n,n-diheptylheptan-1-amine Chemical compound CCCCCCCN(CCCCCCC)CCCCCCC CLZGJKHEVKJLLS-UHFFFAOYSA-N 0.000 description 1
- DIAIBWNEUYXDNL-UHFFFAOYSA-N n,n-dihexylhexan-1-amine Chemical compound CCCCCCN(CCCCCC)CCCCCC DIAIBWNEUYXDNL-UHFFFAOYSA-N 0.000 description 1
- OOHAUGDGCWURIT-UHFFFAOYSA-N n,n-dipentylpentan-1-amine Chemical compound CCCCCN(CCCCC)CCCCC OOHAUGDGCWURIT-UHFFFAOYSA-N 0.000 description 1
- ROZPNEGZBIUWBX-UHFFFAOYSA-N n-[bis(diethylamino)phosphoryl]-n-ethylethanamine Chemical compound CCN(CC)P(=O)(N(CC)CC)N(CC)CC ROZPNEGZBIUWBX-UHFFFAOYSA-N 0.000 description 1
- CQKIJHDQEAQSSZ-UHFFFAOYSA-N n-bis(dibutylamino)phosphoryl-n-butylbutan-1-amine Chemical compound CCCCN(CCCC)P(=O)(N(CCCC)CCCC)N(CCCC)CCCC CQKIJHDQEAQSSZ-UHFFFAOYSA-N 0.000 description 1
- KRGNXJUCIYWFMG-UHFFFAOYSA-N n-bis(dihexylamino)phosphoryl-n-hexylhexan-1-amine Chemical compound CCCCCCN(CCCCCC)P(=O)(N(CCCCCC)CCCCCC)N(CCCCCC)CCCCCC KRGNXJUCIYWFMG-UHFFFAOYSA-N 0.000 description 1
- WAQPJHNWYPETBC-UHFFFAOYSA-N n-bis(dipropylamino)phosphoryl-n-propylpropan-1-amine Chemical compound CCCN(CCC)P(=O)(N(CCC)CCC)N(CCC)CCC WAQPJHNWYPETBC-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- PSCYIXYFSXAVKV-UHFFFAOYSA-N n-butyl-n-[(dibutylamino)-(dimethylamino)phosphoryl]butan-1-amine Chemical compound CCCCN(CCCC)P(=O)(N(C)C)N(CCCC)CCCC PSCYIXYFSXAVKV-UHFFFAOYSA-N 0.000 description 1
- MTHFROHDIWGWFD-UHFFFAOYSA-N n-butyl-n-methylbutan-1-amine Chemical compound CCCCN(C)CCCC MTHFROHDIWGWFD-UHFFFAOYSA-N 0.000 description 1
- GMTCPFCMAHMEMT-UHFFFAOYSA-N n-decyldecan-1-amine Chemical compound CCCCCCCCCCNCCCCCCCCCC GMTCPFCMAHMEMT-UHFFFAOYSA-N 0.000 description 1
- WOLFCKKMHUVEPN-UHFFFAOYSA-N n-ethyl-n-methylbutan-1-amine Chemical compound CCCCN(C)CC WOLFCKKMHUVEPN-UHFFFAOYSA-N 0.000 description 1
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 1
- XWCCTMBMQUCLSI-UHFFFAOYSA-N n-ethyl-n-propylpropan-1-amine Chemical compound CCCN(CC)CCC XWCCTMBMQUCLSI-UHFFFAOYSA-N 0.000 description 1
- QHCCDDQKNUYGNC-UHFFFAOYSA-N n-ethylbutan-1-amine Chemical compound CCCCNCC QHCCDDQKNUYGNC-UHFFFAOYSA-N 0.000 description 1
- XCVNDBIXFPGMIW-UHFFFAOYSA-N n-ethylpropan-1-amine Chemical compound CCCNCC XCVNDBIXFPGMIW-UHFFFAOYSA-N 0.000 description 1
- PXSXRABJBXYMFT-UHFFFAOYSA-N n-hexylhexan-1-amine Chemical compound CCCCCCNCCCCCC PXSXRABJBXYMFT-UHFFFAOYSA-N 0.000 description 1
- CWYZDPHNAGSFQB-UHFFFAOYSA-N n-propylbutan-1-amine Chemical compound CCCCNCCC CWYZDPHNAGSFQB-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002899 organoaluminium compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000011990 phillips catalyst Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- WXYNMTGBLWPTNQ-UHFFFAOYSA-N tetrabutoxygermane Chemical compound CCCCO[Ge](OCCCC)(OCCCC)OCCCC WXYNMTGBLWPTNQ-UHFFFAOYSA-N 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- VALAJCQQJWINGW-UHFFFAOYSA-N tri(propan-2-yl)alumane Chemical compound CC(C)[Al](C(C)C)C(C)C VALAJCQQJWINGW-UHFFFAOYSA-N 0.000 description 1
- MWNSUONCJRRKFE-UHFFFAOYSA-N tributyl(chloro)germane Chemical compound CCCC[Ge](Cl)(CCCC)CCCC MWNSUONCJRRKFE-UHFFFAOYSA-N 0.000 description 1
- JYVWRCIOZLRMKO-UHFFFAOYSA-N tributyl(hydroxy)silane Chemical compound CCCC[Si](O)(CCCC)CCCC JYVWRCIOZLRMKO-UHFFFAOYSA-N 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- KTSWILXIWHVQLR-UHFFFAOYSA-N tributylgermane Chemical compound CCCC[GeH](CCCC)CCCC KTSWILXIWHVQLR-UHFFFAOYSA-N 0.000 description 1
- LHHPEAQVCCPLBC-UHFFFAOYSA-N tributyltin;hydrate Chemical compound O.CCCC[Sn](CCCC)CCCC LHHPEAQVCCPLBC-UHFFFAOYSA-N 0.000 description 1
- YGRHYJIWZFEDBT-UHFFFAOYSA-N tridecylaluminum Chemical compound CCCCCCCCCCCCC[Al] YGRHYJIWZFEDBT-UHFFFAOYSA-N 0.000 description 1
- XBEXIHMRFRFRAM-UHFFFAOYSA-N tridodecylalumane Chemical compound CCCCCCCCCCCC[Al](CCCCCCCCCCCC)CCCCCCCCCCCC XBEXIHMRFRFRAM-UHFFFAOYSA-N 0.000 description 1
- WVMSIBFANXCZKT-UHFFFAOYSA-N triethyl(hydroxy)silane Chemical compound CC[Si](O)(CC)CC WVMSIBFANXCZKT-UHFFFAOYSA-N 0.000 description 1
- IDZOEUNVBFFQNV-UHFFFAOYSA-N triethyl(iodo)germane Chemical compound CC[Ge](I)(CC)CC IDZOEUNVBFFQNV-UHFFFAOYSA-N 0.000 description 1
- LTLGQZPDSQYFSB-UHFFFAOYSA-N triethylgermane Chemical compound CC[GeH](CC)CC LTLGQZPDSQYFSB-UHFFFAOYSA-N 0.000 description 1
- KQPIFPBKXYBDGV-UHFFFAOYSA-M triethylstannanylium;bromide Chemical compound CC[Sn](Br)(CC)CC KQPIFPBKXYBDGV-UHFFFAOYSA-M 0.000 description 1
- PRFPAWZEYOPUKM-UHFFFAOYSA-M triethylstannanylium;iodide Chemical compound CC[Sn](I)(CC)CC PRFPAWZEYOPUKM-UHFFFAOYSA-M 0.000 description 1
- OLBXOAKEHMWSOV-UHFFFAOYSA-N triethyltin;hydrate Chemical compound O.CC[Sn](CC)CC OLBXOAKEHMWSOV-UHFFFAOYSA-N 0.000 description 1
- XJRJIMRCXVCEFA-UHFFFAOYSA-N trihexyl(iodo)germane Chemical compound CCCCCC[Ge](I)(CCCCCC)CCCCCC XJRJIMRCXVCEFA-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- AYVFJPRMOZTEOZ-UHFFFAOYSA-N trihexyltin Chemical compound CCCCCC[Sn](CCCCCC)CCCCCC AYVFJPRMOZTEOZ-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- AEOGRWUNSVGMMJ-UHFFFAOYSA-N trimethylgermane Chemical compound C[GeH](C)C AEOGRWUNSVGMMJ-UHFFFAOYSA-N 0.000 description 1
- AAPLIUHOKVUFCC-UHFFFAOYSA-N trimethylsilanol Chemical compound C[Si](C)(C)O AAPLIUHOKVUFCC-UHFFFAOYSA-N 0.000 description 1
- MZGUIAFRJWSYJJ-UHFFFAOYSA-M trimethylstannanylium;bromide Chemical compound C[Sn](C)(C)Br MZGUIAFRJWSYJJ-UHFFFAOYSA-M 0.000 description 1
- XGRPNCOKLIMKBN-UHFFFAOYSA-M trimethylstannanylium;iodide Chemical compound C[Sn](C)(C)I XGRPNCOKLIMKBN-UHFFFAOYSA-M 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- NEOBYMRDDZMBSE-UHFFFAOYSA-M trioctylstannanylium;hydroxide Chemical compound [OH-].CCCCCCCC[Sn+](CCCCCCCC)CCCCCCCC NEOBYMRDDZMBSE-UHFFFAOYSA-M 0.000 description 1
- CSZJVCVUPYDGNQ-UHFFFAOYSA-N triphenyl(triphenylgermyloxy)germane Chemical compound C=1C=CC=CC=1[Ge](C=1C=CC=CC=1)(C=1C=CC=CC=1)O[Ge](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 CSZJVCVUPYDGNQ-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- NXHORDQDUDIXOS-UHFFFAOYSA-N triphenylgermane Chemical compound C1=CC=CC=C1[GeH](C=1C=CC=CC=1)C1=CC=CC=C1 NXHORDQDUDIXOS-UHFFFAOYSA-N 0.000 description 1
- AIRGWNCSDJWTBV-UHFFFAOYSA-N triphenylgermanium;hydrate Chemical compound O.C1=CC=CC=C1[Ge](C=1C=CC=CC=1)C1=CC=CC=C1 AIRGWNCSDJWTBV-UHFFFAOYSA-N 0.000 description 1
- NLSXASIDNWDYMI-UHFFFAOYSA-N triphenylsilanol Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(O)C1=CC=CC=C1 NLSXASIDNWDYMI-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- FHJWZJDDIKLZPD-UHFFFAOYSA-N tripropylgermane Chemical compound CCC[GeH](CCC)CCC FHJWZJDDIKLZPD-UHFFFAOYSA-N 0.000 description 1
- GQBRIYIRPORZOM-UHFFFAOYSA-M tripropylstannanylium;bromide Chemical compound CCC[Sn](Br)(CCC)CCC GQBRIYIRPORZOM-UHFFFAOYSA-M 0.000 description 1
- GGSUJMOTNBEZHS-UHFFFAOYSA-M tripropylstannanylium;hydroxide Chemical compound [OH-].CCC[Sn+](CCC)CCC GGSUJMOTNBEZHS-UHFFFAOYSA-M 0.000 description 1
- MHTXEMSDIHFLFI-UHFFFAOYSA-M tripropylstannanylium;iodide Chemical compound CCC[Sn](I)(CCC)CCC MHTXEMSDIHFLFI-UHFFFAOYSA-M 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
Definitions
- the present invention relates to a catalyst suitable for use in the production of olefin, especially ethylene, polymers or copolymers by the polymerization of ethylene, or components containing, as a main constituent, ethylene.
- U.S. Pat. No. 3,752,795 discloses a process for polymerizing polyolefins in the presence of (i) chromyl bis(triorganotitanates) having the general formula: ##STR1## wherein R is an alkylalkaryl, aryl or cycloalkyl group and (ii) an organoaluminum compound.
- chromyl bis(triorganotitanates) having the general formula: ##STR1## wherein R is an alkylalkaryl, aryl or cycloalkyl group and (ii) an organoaluminum compound.
- Japanese Patent Application Laid-Open (Kokai) No. 51-116192/1976 discloses the combined use of a catalyst comprising a solid inorganic supporting material having a surface hydroxyl group, a reaction product of chromium trioxide and a phosphorus compound, and an aluminum compound with a reducing agent (e.g. a boron compound).
- An object of the present invention is to provide a catalyst suitable for use in the polymerization of olefins, which catalyst has a high activity and is capable of producing olefin polymers or copolymers having an excellent melt flowability.
- a catalyst for polymerizing olefins comprising:
- R 1 , R 2 and R 3 are each independently a hydrocarbon group having 1 through 10 carbon atoms, and R 4 is a hydrogen atom, a halogen atom, --OH group, or --OGeR 1 R 2 R 3 group or (ii) R 1 , R 2 , R 3 and R 4 are each independently --OR 5 wherein R 5 is a hydrocarbon group having 1 through 10 carbon atoms, or a halogen atom, and a tin compound having the general formula:
- R 1 , R 2 and R 3 are the same as defined above and R 6 is a halogen atom, or --OH group, with (b) at least one chromium compound, said reaction product being supported on an inorganic oxide carrier; and
- M is an element selected from aluminum, boron, beryllium, zinc or lithium;
- R 7 and R 8 are the same or different hydrocarbon groups having 1 to 20 carbon atoms;
- X and Y are the same of different groups selected from OR 7 , OSiR 10 R 11 R 12 , NR 13 R 14 , or SR 15 wherein R 9 , R 10 , R 11 , R 12 , R 13 , and R 14 are independently hydrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms, and R 15 is a hydrocarbon group having 1 to 20 carbon atoms;
- ⁇ is zero or greater than zero, ⁇ is greater than zero, and
- an organoaluminum component obtained by reacting (i) one mole of a trialkylaluminum compound with (ii) 0.1 to 2 moles of a carbinol having 1 to 10 carbon atoms, 0.1 to 5 moles of a silanol or siloxane, or a mixture thereof;
- a component comprising said organoaluminum component (2) and an organoboron, organozinc, or organolithium compound.
- the catalyst according to the present invention has the following remarkable, advantageous features:
- the molecular weight of the polymer can be controlled by slurry polymerization at a temperature of 100° C. or less, and the activity of the catalyst, in terms of the amount of polymers produced per 1 g of the catalyst, is high and the catalyst residue treatment step can be omitted;
- the particle size of the resultant polymer can be controlled and a polymer having a large particle size can be obtained.
- the inorganic oxide carriers usable in the present invention include, for example, silica, silica-alumina, alumina, thoria, and zirconia.
- the preferred inorganic oxide carriers are silica and silica-alumina.
- the silica carriers those having a specific surface area of 200 through 600 m 2 /g, determined by the BET method, a specific pore volume of 1 through 2 ml/g, and an average pore diameter of 50 through 300 ⁇ are especially preferable in the practice of the present invention.
- the water content of the carrier is desirably 0.01 through 1% by weight, more desirably 0.1 through 0.8% by weight.
- the carrier is desirably dried prior to the supporting of the chromium compound.
- the carriers are desirably dried at a temperature of 100° C. or more, more desirably 200° through 1000° C., for several minutes through several tens of hours, more desirably 30 minutes through 20 hours, under a reduced pressure in an inert gas (such as oxygen, nitrogen, helium, or air) environment, containing no substantial amount of water. Drying is desirably carried out under a solid in a fluidized state in the presence of a sufficient amount of inert gas.
- an inert gas such as oxygen, nitrogen, helium, or air
- the chromium compounds usable in the present invention include, for example, chromium trioxide, chromic acid, silver chromate, potassium chromate, sodium chromate, magnesium chromate, and calcium chromate. These chromium compounds are desirably used in the present invention after purification is carried out.
- the amine compounds usable in the present invention include: for example, aliphatic amines such as ethylamine, propylamine, butylamine, amylamine, hexylamine, cyclohexylamine, octylamine, decylamine, methylethylamine, methylbutylamine, diethylamine, dipropylamine, dibutylamine, dihexylamine, dicyclohexylamine, dioctylamine, didecylamine, ethylpropylamine, ethylbutylamine, propylbutylamine, methyldiethylamine, methylethylbutylamine, methyldibutylamine, triethylamine, ethyldipropylamine, tripropylamine, tributylamine, triamylamine, trihexylamine, and triheptylamine; aromatic amines such
- the phosphoric amide compounds usable in the present invention include: for example, aliphatic phosphoric triamides such as hexamethylphosphoric triamide, hexaethylphosphoric triamide, hexapropylphosphoric triamide, hexabutylphosphoric triamide, hexahexylphosphoric triamide, and N,N-dimethyl-N',N',N",N"-tetrabutylphosphoric triamide; aromatic phosphoric triamides such as N,N',N"-triphexylphosphoric triamide and N,N',N"-trinaphtylphosphoric triamide; and phosphoric diamides such as phosphoric acid dianilide. Aliphatic phosphoric triamides are desirably used in the present invention.
- a chromium compound such as chromium trioxide with amines or phosphoric amides
- hydrocarbons are methylene chloride, chloroform, carbon tetrachloride, benzene, toluene, pentane, hexane, heptane, and cyclohexane.
- the reaction of a chromium compound such as chromium trioxide with amines or phosphoric amides is desirably carried out at a mol ratio of the chromium compound to the amines or the phosphoric amides of 1:0.1 through 1:10 at a temperature of 10° through 100° C., desirably 20° through 80° C., for several minutes through 20 hours, desirably 10 minutes through 5 hours.
- the use of too small an amount of the chromium compound results in only a small amount of the reaction product. Contrary to this, the use of too large an amount of the chromium compound results in an increase in the amount of the unreacted chromium compound.
- hydrocarbyloxy compounds of titanium, vanadium, hafnium and zirconium will now be explained.
- hydrocarbyloxy compounds of titanium usable in the present invention are those having the general formula:
- R 16 is a hydrocarbon group having 1 through 20 carbon atoms
- X is a halogen atom
- l is a number of 1 through 4 (i.e. 1 ⁇ l ⁇ 4).
- R 16 groups are methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, phenyl, tolyl, and cyclohexyl.
- l is 2 ⁇ l ⁇ 4, and more desirably, l is 3 ⁇ l ⁇ 4.
- X is desirably chlorine.
- hydrocarbyloxy compounds of zirconium usable in the present invention are those having the general formula:
- R 16 , X, and l are the same as defined above.
- l is 2 ⁇ l ⁇ 4, and more desirably, l is 3 ⁇ l ⁇ 4.
- X is desirably chlorine.
- Examples of the desirable compounds are Zr(OC 3 H 7 ) 4 , Zr(OC 4 H 9 ) 4 , Zr(OC 5 H 11 ) 4 , Zr(OC 6 H 5 ) 4 , and Zr(OC 4 H 9 ) 3 Cl.
- hydrocarbyloxy compounds of hafnium usable in the present invention are those having the general formula:
- R 16 , and X are the same as defined above, and l is a number of 1 through 3 (i.e. 1 ⁇ l ⁇ 3).
- chromium compounds such as chromium trioxide with hydrocarbyloxy compounds of titanium, vanadium, zirconium, and hafnium
- hydrocarbyloxy compounds of titanium, vanadium, zirconium, and hafnium can be carried out in the presence of an inert organic solvent.
- the presence of oxygen and water in the reaction medium is not desirable and, therefore, the contamination of the reaction medium with oxygen and water should be avoided. Furthermore, the exposure of the reaction medium to light also is not desirable.
- the unreacted chromium compounds are desirably removed from the reaction mixture. It appears that the reaction product contains compounds having the following structure: ##STR2##
- the germanium compounds having the general formula R 1 R 2 R 3 R 4 Ge and usable in the present invention consist of two groups.
- R 1 , R 2 and R 3 in the general formula are each independently a hydrocarbon group having 1 through 10 carbon atoms
- R 4 is a hydrogen atom, a halogen atom, --OH group, or --OGeR 1 R 2 R 3 group
- R 1 , R 2 , R 3 and R 4 in the general formula are each independently --OR 5 wherein R 5 is a hydrocarbon group having 1 through 10 carbon atoms or a halogen atom, provided that R 1 , R 2 , R 3 and R 4 are not all halogen atoms.
- R 1 , R 2 and R 3 in the general formula are independently a hydrocarbon group having 1 to 10 carbon atoms.
- examples of such groups are: for example, aliphatic hydrocarbon groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, and decylgroups; and aromatic hydrocarbon groups such as phenyl and tolyl groups.
- the aromatic hydrocarbon groups are desirably used in the present invention.
- R 4 in the general formula is a hydrogen atom, a halogen atom, --OH, or --OGeR 1 R 2 R 3 .
- the halogen atom includes Cl, Br, or I, desirably Br.
- Examples of these compounds are trimethyl-germane, trimethylchlorogermane, trimethylbromogermane, trimethyliodogermane, bis-trimethylgermoxane, triethylgermane, triethylchlorogermane, triethylbromogermane, triethyliodogermane, bis-triethylgermoxane, tripropylgerman, tripropylchlorogermane, tripropylbromogermane, tripropyliodogermane, bis-tripropylgermoxane, tributylgermane, tributylchlorogermane, tributylbromogermane, tributyliodogermane, bis-tributylgermoxane, trihexylgerman, trihexylchlorogermane, trihexyl-bronogerman, trihexylio
- R 1 , R 2 , R 3 and R 4 in the general formula are independently --OR 5 or a halogen atom wherein R 5 is a hydrocarbon group having 1 to 10 carbon atoms.
- R 5 are methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, phenyl, tolyl, and cyclohexyl.
- the halogen atom is chlorine, bromine, or iodide, desirably chlorine.
- the number of the halogen atoms per germanium atom is 0 through 3, desirably 0 through 2 and more desirably 0 through 1. Accordingly, especially desirable compounds are represented by the general formulae: (R 5 O) 3 GeCl and (R 5 O) 4 Ge.
- the tin compounds usable in the present invention are those having the general formula R 1 R 2 R 3 R 6 Sn wherein R 1 , R 2 and R 3 are the same as defined above and R 6 is halogen atom or a --OH group.
- the halogen atom includes Cl, Br, or I, desirably Cl or Br.
- tin compounds are trimethylchlorotin, trimethylbromotin, trimethyliodotin, trimethyltin hydroxide, triethylchlorotin, triethylbromotin, triethyliodotin, triethyltin hydroxide, tripropylchlorotin, tripropylbromotin, tripropyliodotin, tripropyltin hydroxide, tributylchlorotin, tributylbromotin, tributyliodotin, tributyltin hydroxide, trihexylchlorotin, trihexylbromotin, trihexyliodotin, trihexyltin hydroxide, trioctylchlorotin, trioctylbromotin, trioctyliodotin, trioctyltin hydroxide, tridecyl
- the reaction of the first group of germanium compounds with the chromium compounds is, for example, those of (1) a trialkylbromogermane or triarylbromogermane with silver chromate, (2) a bis-trialkylgermoxane or bis-triarylgermoxane with chromic acid, (3) a triarylgermanol with chromium trioxide, and a trialkylgermane or triarylgermane with chromic acid.
- the reaction medium are methylene chloride, chloroform, carbon tetrachloride, benzene, toluene, pentane, hexane, heptane, and cyclohexane.
- the reaction of the first group of germanium compounds with the chromium compounds is desirably carried out at a mol ratio of the germanium compounds to the chromium compounds of 1:0.1 through 1:10 at a temperature of 10° through 100° C., desirably 20° through 80° C., for several minutes through 20 hours, desirably 10 minutes through 5 hours.
- the use of too small an amount of the chromium compounds results in only a small amount of the reaction product. Contrary to this, the use of too large an amount of the chromium compounds results in an increase in the amount of the unreacted chromium compounds.
- the presence of a small amount of water in the reaction medium can desirably accelerate the reaction. It is estimated from the literature (e.g. Z. Chem. 20, 31, 1980) that the compounds obtained from the above-mentioned reaction are germanium chromates having the general formula: ##STR3##
- chromium trioxide is most desirably used as a chromium compound.
- the reaction is desirably carried out in a reaction solvent such as, for example, methylene chloride, chloroform, carbon tetrachloride, benzene, toluene, pentane, hexane, heptane, and cyclohexane.
- the desirable mol ratio of the germanium compound to chromium trioxide in the reaction is 1:0.1 through 1:10.
- the use of a chromium compounds in an amount less than the above range results in only a small amount of the reaction product.
- the reaction is generally carried out at a temperature of 10° through 100° C., desirably 20° through 80° C., for a dozen or so minutes through 50 hours, desirably 30 minutes through 30 hours. It is estimated that the reaction product contains compounds having the following general formula: ##STR4##
- Examples of the reaction of tin compounds having the general formula R 1 R 2 R 3 R 4 Sn with chromium compounds are (1) a trialkylhalogenotin or triarylhalogenotin with silver chromate and (2) a trialkyltin hydroxide or triaryltin hydroxide with chromium trioxide.
- the reaction solvents usable in the reaction of the germanium compounds with the chromium compounds can also be used in this reaction.
- the reaction mol ratio, the reaction temperature and the reaction time period in respect to this reaction are also substantially the same as in the case of the germanium compounds. It is also estimated from the known literature (e.g. Z. Chem. 20, 31, 1980) that the reaction product contains compounds having the general formula: ##STR5##
- the above-mentioned reaction products can be supported on an inorganic oxide carrier such as silica in any conventional manner.
- the inorganic oxide carrier substance is impregnated with a solution of the above-mentioned reaction product, followed by either vaporization (or distillation) of the solvent or filtration of the solution.
- the former is preferred.
- Supporting is generally carried out at a temperature of -10° through 70° C., desirably 0° through 55° C.
- the chromium compounds are supported on the carrier in an amount of 0.01 through 10% by weight, desirably 0.05 through 5% by weight and more desirably 0.1 through 3% by weight.
- the supported solid obtained above is calcined and activated. This activation is generally carried out in the presence of oxygen. It is especially important that the water content of the atmosphere be low when the supported solid is calcined.
- the water content of the atmosphere should be 20 ppm or less, desirably 10 ppm or less and more desirably 1 ppm or less.
- Calcination can be carried out under an inert gas atmosphere or under a reduced pressure. However, calcination is preferably carried out under an oxidizing atmosphere, such as air.
- Activation of the supported solid by calcination is carried out at a temperature of 300° through 900° C., desirably 500° through 800° C.
- the activation time is generally 0.5 through 10 hours; however, it depends upon the activation temperature.
- organometallic compound component (B) usable, together with the solid catalyst component (A), in the present invention will now be explained.
- the organomagnesium compound component usable in the present invention includes hydrocarbon-soluble organomagnesium compounds having the general formula:
- M is an element selected from aluminum, boron, beryllium, zinc or lithium;
- R 7 and R 8 are the same or different hydrocarbon groups having 1 to 20 carbon atoms;
- examples of the hydrocarbon groups represented by R 7 through R 15 are alkyl groups, desirably having 1 to 20 carbon atoms, cycloalkyl groups, desirably having 3 to 10 carbon atoms, or aryl groups, desirably having 6 to 20 carbon atoms.
- Typical examples of such groups are methyl, ethyl, propyl, butyl, amyl, hexyl, decyl, cyclohexyl, and phenyl groups.
- R 7 is desirably an alkyl group
- R 9 through R 14 may be a hydrogen atom
- R 9 is desirably a hydrogen atom.
- the metal M In the case of ⁇ >0, aluminum, boron, zinc, beryllium and lithium are desirably used as the metal M since these metals readily form hydrocarbon-soluble organomagnesium complexes.
- the ratio of magnesium to the metallic atom M i.e. ⁇ / ⁇ is desirably 0.2 or more and more desirably 0.5 or more although there is no critical limitation of this ratio.
- the relationship (r+s)/( ⁇ + ⁇ ), which means a ratio of the total number of X and Y to the total number of metallic atoms, is generally 0 ⁇ (r+s)/( ⁇ + ⁇ ) ⁇ 1.5, desirably 0 ⁇ (r+s)/( ⁇ + ⁇ ) ⁇ 1.0 and more desirably 0 ⁇ (r+s)/( ⁇ + ⁇ ) ⁇ 0.8.
- organomagnesium complex compounds usable in the present invention are synthesized by reacting an organomagnesium compound represented by the general formula R 7 MgX or R 7 2 Mg, wherein R 7 is the same as defined above and X is a halogen, with an organometallic compound represented by MR 8 m or MR 8 m-1 H, wherein M, R 8 and m are the same as defined above, at a temperature ranging from room temperature to 150° C. in an inert hydrocarbon solvent, such as hexane, heptane, cyclohexane, benzene, and toluene.
- an organomagnesium compound represented by the general formula R 7 MgX or R 7 2 Mg wherein R 7 is the same as defined above and X is a halogen
- organometallic compound represented by MR 8 m or MR 8 m-1 H wherein M, R 8 and m are the same as defined above
- organomagnesium compounds can also be synthesized by the reaction of (i) MgX 2 and MR 8 m or MR 8 m-1 H or (ii) R 7 MgX or MgR 7 2 and R 8 n MX m-n wherein M, R 7 and R 8 are the same as defined above and n is a number of 0 through m.
- organomagnesium compounds that is, the hydrocarbon-soluble organomagnesium compounds having the general formula MgR 7 p R 8 q , the following three groups are generally involved.
- At least one of R 7 and R 8 is a secondary or tertially alkyl group having 4 to 6 carbon atoms;
- R 7 and R 8 are alkyl groups having different carbon atoms
- At least one of R 7 and R 8 is a hydrocarbon group having 6 or more carbon atoms.
- Both R 7 and R 8 are alkyl groups having 4 to 6 carbon atoms and at least one of R 7 and R 8 is a secondary or tertially alkyl group.
- R 7 is an alkyl group having 2 or 3 carbon atoms and R 8 is an alkyl group having 4 or more carbon atoms.
- R 7 and R 8 are alkyl groups having 6 or more carbon atoms.
- the secondary alkyl groups or the tertially alkyl groups having 4 to 6 carbon atoms in the above-mentioned cases (a) and (a') include, for example, sec-C 4 H 9 , tert-C 4 H 9 , --CH(C 2 H 5 ) 2 , --C(C 2 H 5 )(CH 3 ) 2 , --CH(CH 3 )(C 4 H 9 ), --CH(C 2 H 5 )(C 3 H 7 ), --(CH 3 ) 2 (C 3 H 7 ), and --C(CH 3 )(C 2 H 5 ) 2 .
- the desirable group is a secondary alkyl group, especially the sec--C 4 H 9 group.
- the alkyl groups having 2 or 3 carbon atoms in the above-mentioned cases (b) and (b') include, for example, ethyl and propyl groups, desirably the ethyl group.
- the alkyl groups having 4 or more carbon atoms include, for example, butyl, amyl, hexyl and octyl groups, desirably the butyl and hexyl groups.
- the hydrocarbon groups having 6 or more carbon atoms in the above-mentioned cases (c) and (c') include, for example, an alkyl group, such as hexyl, octyl, or decyl group, and a phenyl group, desirably a hexyl group.
- organomagnesium compounds examples include (sec--C 4 H 9 ) 2 Mg, (tert--C 4 H 9 ) 2 Mg, n--C 4 H 9 --Mg--C 2 H 5 , n--C 4 H 9 --Mg--sec--C 4 H 9 , n--C 4 H 9 --Mg--tert--C 4 H 9 , n--C 6 H 13 --Mg--C 2 H 5 , (n--C 6 H 13 ) 2 Mg, (n--C 8 H 17 ) 2 Mg, and (n--C 10 H 21 ) 2 Mg.
- the organoaluminum compound conponents usable in the present invention include, for example, components obtained by reacting and/or mixing trialkylaluminum compounds with carbinols and/or silanols or hydrosiloxy compounds.
- the carbinols having 1 to 10 carbon atoms include, for example, methyl alcohol, ethyl alcohol, n-and iso-propyl alcohol, n-, iso-and tert-butyl alcohol, n-, iso-, sec-and tert-amyl alcohol, phenol, and cresol.
- the reaction ratio of the carbinol to the trialkylaluminum is 0.1 through 2 moles, desirably 0.15 through 1.5 moles and most desirably 0.2 through 1.3 moles, based on 1 mol of trialkylaluminum.
- the reaction ratio of the silanols or hydrosiloxy compounds to the trialkylaluminum is 0.1 through 5 moles, desirably 0.1 through 2 moles and most desirably 0.2 through 1.5 moles, based on 1 mol of the trialkylaluminum.
- the ratio of the organoaluminum component to the organomagnesium component is 0.05 through 50 moles, desirably 0.1 through 10 moles, based on 1 mol of the organomagnesium component.
- the organomagnesium component and the organoaluminum component can be added to a polymerization mixture separately or in the form of a mixture obtained from previous mixing of the organomagnesium component and the organoaluminum component. Previous contact between the solid catalyst component and a small amount of the component (B) prior to its addition to the polymerization mixture provides a good result.
- the ratio of the component (B) to the component (A) in terms of the metals (gr. atom) in the component (B)/CR (gr. atom) in the component (A) is generally 0.01 through 3000, desirably 0.1 through 100.
- the catalyst according to the present invention is suitably used in the polymerization of ethylene or in the copolymerization of ethylene in which ethylene is a main constituent.
- Monomers usable in the copolymerization of ethylene are mono-olefins or diolefins having 3 to 12 carbon atoms.
- Examples of such monomers are propylene, butene-1, pentene-1, 3-methylbutene-1, hexene-1, 4-methylpentene-1, 3-ethylbutene-1, heptene-1, octene-1, decene-1, butadiene, isoprene, 1,4-hexadiene, 1,5-hexadiene, 1,7-octadiene, dicyclopentadiene, and ethylidene norbornene.
- One or two of these monomers can be used in the copolymerization of ethylene.
- the density of the ethylene polymers or ethylene copolymers produced by using the present catalyst is approximately 0.91 through 0.97.
- Polymerization can be carried out in any conventional manner, including suspension polymerization, bulk polymerization, solution polymerization, and gas phase polymerization.
- the polymerization reaction can be generally carried out at a temperature ranging, for example, from room temperature to approximately 300° C.
- the polymerization conditions depend upon the polymerization pressure, the partial pressure of the moomer, and the kinds and concentrations of the catalyst components.
- polymerization is carried out in a slurry state at a temperature ranging from room temperature through 100° C. and in a solution state at a temperature of 100° through 200° C.
- Polymerization is desirably carried out in a slurry state.
- polymerization may be carried out under a gas phase condition substantially in the absence of an inert organic solvent.
- hydrocarbon solvents are desirably used.
- organic hydrocarbon solvents are: aliphatic saturated hydrocabons, such as butane, isobutane, pentane, hexane, heptane, octane, isooctane, decane, and purified kerosene; alicyclic saturated hydrocarbons, such as cyclopentane, cyclohexane, dimethylcyclopentane, and methylcyclohexane; and aromatic hydrocarbons, such as benzene, toluene, and xylene.
- Desirable hydrocarbon solvents are isobutane, pentane, hexane, heptane, and cyclohexane.
- Polymerization may be carried out in the presence of a molecular weight modifier, such as hydrogen, and halogenated hydrocarbons, desirably hydrogen.
- a molecular weight modifier such as hydrogen, and halogenated hydrocarbons, desirably hydrogen.
- the amount of the molecular weight modifier can be optionally controlled as required.
- Polymerization can be carried out by means of a conventional one-stage polymerization method using one reaction zone or by means of a so-called multi-stage polymerization method using a plurality of reaction zones.
- the polymers obtained by using the present catalyst have a wide molecular weight distribution and a relatively high molecular weight, even when obtained by using a one-stage polymerization method, and, therefore, are especially suitable for use in blow molding and film molding.
- Polymers having an additionally wide molecular weight distribution can be produced by means of multi-stage polymerization in which two or more polymerization conditions are used.
- the catalyst efficiency was 2700 g-polyethylene (PE)/ g-solid catalyst hr, MI of the polymer was 0.1 g/10 min and FR was 255.
- Example 1 was repeated, except that an organoaluminum compound obtained in the following manner was used in lieu of the organoaluminum compound synthesized in Example 1.
- Ethylene was polymerized in the same manner as in Example 1, except that the above-prepared solid catalyst component was used.
- Catalyst efficiency 2400 g-PE/g-solid catalyst.hr
- Example 1 To 100 mg of the solid catalyst component obtained in Example 1, 0.01 m mol of an orgianomagnesium component Mg 6 .0 (n-C 4 H 9 ) 12 (C 2 H 5 ) 3 .0 (a 1 mol/l solution in hexane) and 0.01 m mol of an organoaluminium compound Al(C 2 H 5 ) 2 (OSiH.CH 3 .C 2 H 5 ) (a 1 mol/l solution in hexane) was added and the mixture was allowed to react at a room temperature for 1 day. The polymerization of ethylene in Example 1 was repeated except that the catalyst prepared above was used in lieu of the catalyst of Example 1.
- Ethylene was polymerized in the same manner as in Example 1 except that an organomagnesium component and an organoaluminum compound were changed as shown in Table 1.
- Ethylene was polymerized in the same manner as in Example 1 except that the compounds listed in Table 2 below were used. The results are also shown in Table 2.
- Ethylene was polymerized in the same manner as in Example 1 except that the components (B) listed in Table 3 were used.
- the solid catalyst component was prepared in the same manner as in Example 1.
- Silica (Davison 952®) was dried at a temperature of 800° C. for 4 hours in a dry nitrogen stream. 5 g of the dried silica was charged, together with 20 ml of CH 2 Cl 2 , into a 100 ml flask purged with nitrogen. 14.6 ml of the solution obtained in (1) above was dropwise added to the flask at a room temperature under stirring. After stirring for 30 minutes, CH 2 Cl 2 was distilled off under a reduced pressure. The resultant solid was calcined at a temperature of 800° C. for 4 hours in a dry air fluidized state. Thus, the solid catalyst component was obtained.
- the catalyst activity was 560,000 g/g. Cr atom, MI 0.34 g/10 min., FR 90 and the bulk density 0.42 g/c.c.
- Ethylene was polymerized in the same manner as in Example 26 except that the organomagnesium components and the organoaluminum components listed in Table 4 below were used. The results are shown in Table 4.
- Ethylene was polymerized in the same manner as in Example 26 except that the above-prepared solid catalyst was used. The results are shown in Table 4 below.
- Ethylene was polymerized in the same manner as in Example 26 except that the above-prepared solid catalyst was used. The results are shown in Table 4.
- Ethylene was polymerized in the same manner as in Example 26 except that the above-prepared solid catalyst was used. The results are shown in Table 4.
- Ethylene was polymerized in the same manner as in Example 26 except that the solid catalyst component of Example 34 as well as the organomagnesium component and the organoaluminum component listed in Table 4 were used. The results are shown in Table 4.
- the solid obtained in (2) above was calcined at a temperature of 800° C. for 4 hours in a dry air fluidized state. Thus, a solid catalyst component was obtained.
- the catalyst activity was 629,000 g/g.Cr atom, MI 0.23 g/10 min and FR 140.
- the particle size distribution of the polymer was such that 20 mesh up was 21%, 28 mesh up 39%, and 35 mesh up 21%.
- the resultant polymer had a large particle size, more than 80% of which particles was a size not passing through a 35 mesh sieve.
- Ethylene was polymerized in the same manner as in Example 36 except that the compounds listed in Table 5 was used in lieu of the amine compound of Example 36 and the amount of the chromium supported was changed. The results are shown in Table 5 below.
- Ethylene was polymerized in the same manner as in Example 37 except that the amount and the composition of the organomagnesium component were changed. The results are shown in Table 5.
- Ethylene was polymerized in the same manner as in Example 36 except that the organomagnesium component obtained above was used. The results are shown in Table 5.
- an alkoxy-containing organomagnesium component having a composition of AlMg 4 .0 (C 2 H 5 ) 2 .70 (n--C 4 H 9 ) 6 .3 (O--n-Bu) 2 .0 was obtained.
- Ethylene was polymerized in the same manner as in Example 36 except that the organomagnesium compound obtained above was used. The results are shown in Table 5 below.
- Ethylene was polymerized in the same manner as in Example 36 except that organometallic compound components listed in Table 5 were used. The results are shown in Table 5.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
A catalyst suitable for use in the polymerization of olefins is disclosed. This catalyst contains:
[A] a solid catalyst component obtained by calcining a reaction product of (a) at least one compound selected from an amine compound, a phosphoric acid amide, a hydrocarbyloxy compound of titanium, vanadium, hafnium or zirconium, and a germanium compound having the general formula:
R.sup.1 R.sup.2 R.sup.3 R.sup.4 Ge
wherein (i) R1, R2 and R3 are each independently a hydrocarbon group having 1 through 10 carbon atoms, and R4 is a hydrogen atom, a halogen atom, a --OH group, or a --OGeR1 R2 R3 group, or (ii) R1, R2, R3 and R4 are each independently --OR5 wherein R5 is a hydrocarbon group having 1 through 10 carbon atoms, or a halogen atom, and a tin compound having the general formula:
R.sup.1 R.sup.2 R.sup.3 R.sup.6 Sn
wherein R1, R2 and R3 are the same as defined above and R6 is a halogen atom, or --OH group, with (b) at least one chromium compound, said reaction product being supported on an inorganic oxide carrier; and
[B] an organometallic compound component.
Description
The present invention relates to a catalyst suitable for use in the production of olefin, especially ethylene, polymers or copolymers by the polymerization of ethylene, or components containing, as a main constituent, ethylene.
U.S. Pat. No. 3,752,795 discloses a process for polymerizing polyolefins in the presence of (i) chromyl bis(triorganotitanates) having the general formula: ##STR1## wherein R is an alkylalkaryl, aryl or cycloalkyl group and (ii) an organoaluminum compound. Furthermore, Japanese Patent Application Laid-Open (Kokai) No. 51-116192/1976 discloses the combined use of a catalyst comprising a solid inorganic supporting material having a surface hydroxyl group, a reaction product of chromium trioxide and a phosphorus compound, and an aluminum compound with a reducing agent (e.g. a boron compound).
An object of the present invention is to provide a catalyst suitable for use in the polymerization of olefins, which catalyst has a high activity and is capable of producing olefin polymers or copolymers having an excellent melt flowability.
Other objects and advantages of the present invention will be apparent from the description set forth hereinbelow.
In accordance with the present invention, there is provided a catalyst for polymerizing olefins comprising:
A a solid catalyst component obtained by calcining a reaction product of
(a) at least one compound selected from an amine compound, a phosphoric acid amide, a hydrocarbyloxy compound of titanium, vanadium, hafnium or zirconium, and a germanium compound having the general formula:
R.sup.1 R.sup.2 R.sup.3 R.sup.4 Ge
wherein (i) R1, R2 and R3 are each independently a hydrocarbon group having 1 through 10 carbon atoms, and R4 is a hydrogen atom, a halogen atom, --OH group, or --OGeR1 R2 R3 group or (ii) R1, R2, R3 and R4 are each independently --OR5 wherein R5 is a hydrocarbon group having 1 through 10 carbon atoms, or a halogen atom, and a tin compound having the general formula:
R.sup.1 R.sup.2 R.sup.3 R.sup.6 Sn
wherein R1, R2 and R3 are the same as defined above and R6 is a halogen atom, or --OH group, with (b) at least one chromium compound, said reaction product being supported on an inorganic oxide carrier; and
(B) an organometallic compound component selected from the following groups (1) through (5):
(1) a hydrocarbon-soluble organomagnesium component having the general formula:
M.sub.α Mg.sub.β R.sup.7.sub.p R.sup.8.sub.q X.sub.r Y.sub.s
wherein M is an element selected from aluminum, boron, beryllium, zinc or lithium; R7 and R8 are the same or different hydrocarbon groups having 1 to 20 carbon atoms; X and Y are the same of different groups selected from OR7, OSiR10 R11 R12, NR13 R14, or SR15 wherein R9, R10, R11, R12, R13, and R14 are independently hydrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms, and R15 is a hydrocarbon group having 1 to 20 carbon atoms; α is zero or greater than zero, β is greater than zero, and p, q, r, and s are each zero or greater than zero and both p and q are not zero at the same time and have the relationship p+q+r+s=mα+2β wherein m has a valency of M;
(2) an organoaluminum component obtained by reacting (i) one mole of a trialkylaluminum compound with (ii) 0.1 to 2 moles of a carbinol having 1 to 10 carbon atoms, 0.1 to 5 moles of a silanol or siloxane, or a mixture thereof;
(3) a component comprising said hydrocarbon-soluble organomagnesium component (1) and said organoaluminum component (2);
(4) a component comprising said hydrocarbon-soluble organomagnesium component (1) and an organoboron, organozinc, or organolithium compound; and
(5) a component comprising said organoaluminum component (2) and an organoboron, organozinc, or organolithium compound.
The catalyst according to the present invention has the following remarkable, advantageous features:
(1) the molecular weight of the polymer can be controlled by slurry polymerization at a temperature of 100° C. or less, and the activity of the catalyst, in terms of the amount of polymers produced per 1 g of the catalyst, is high and the catalyst residue treatment step can be omitted;
(2) the melt flowability, especially the swelling ratio of the resultant polymer, is excellent; and
(3) the particle size of the resultant polymer can be controlled and a polymer having a large particle size can be obtained.
The inorganic oxide carriers usable in the present invention include, for example, silica, silica-alumina, alumina, thoria, and zirconia. The preferred inorganic oxide carriers are silica and silica-alumina. Of the silica carriers, those having a specific surface area of 200 through 600 m2 /g, determined by the BET method, a specific pore volume of 1 through 2 ml/g, and an average pore diameter of 50 through 300 Å are especially preferable in the practice of the present invention.
The water content of the carrier is desirably 0.01 through 1% by weight, more desirably 0.1 through 0.8% by weight. For this reason, the carrier is desirably dried prior to the supporting of the chromium compound. The carriers are desirably dried at a temperature of 100° C. or more, more desirably 200° through 1000° C., for several minutes through several tens of hours, more desirably 30 minutes through 20 hours, under a reduced pressure in an inert gas (such as oxygen, nitrogen, helium, or air) environment, containing no substantial amount of water. Drying is desirably carried out under a solid in a fluidized state in the presence of a sufficient amount of inert gas.
The chromium compounds usable in the present invention include, for example, chromium trioxide, chromic acid, silver chromate, potassium chromate, sodium chromate, magnesium chromate, and calcium chromate. These chromium compounds are desirably used in the present invention after purification is carried out.
The amine compounds usable in the present invention include: for example, aliphatic amines such as ethylamine, propylamine, butylamine, amylamine, hexylamine, cyclohexylamine, octylamine, decylamine, methylethylamine, methylbutylamine, diethylamine, dipropylamine, dibutylamine, dihexylamine, dicyclohexylamine, dioctylamine, didecylamine, ethylpropylamine, ethylbutylamine, propylbutylamine, methyldiethylamine, methylethylbutylamine, methyldibutylamine, triethylamine, ethyldipropylamine, tripropylamine, tributylamine, triamylamine, trihexylamine, and triheptylamine; aromatic amines such as aniline, toluidine, xylidine, N-methylaniline, diphenylamine, and triphenyl amine; and heterocyclic amines such as pyrrole, pyridine, piperidine, and N-methyl pyrrolidine. Aliphatic amines are desirably used in the present invention.
The phosphoric amide compounds usable in the present invention include: for example, aliphatic phosphoric triamides such as hexamethylphosphoric triamide, hexaethylphosphoric triamide, hexapropylphosphoric triamide, hexabutylphosphoric triamide, hexahexylphosphoric triamide, and N,N-dimethyl-N',N',N",N"-tetrabutylphosphoric triamide; aromatic phosphoric triamides such as N,N',N"-triphexylphosphoric triamide and N,N',N"-trinaphtylphosphoric triamide; and phosphoric diamides such as phosphoric acid dianilide. Aliphatic phosphoric triamides are desirably used in the present invention.
The reaction of a chromium compound such as chromium trioxide with amines or phosphoric amides can be desirably carried out in an inert hydrocarbon medium. Examples of such hydrocarbons are methylene chloride, chloroform, carbon tetrachloride, benzene, toluene, pentane, hexane, heptane, and cyclohexane. The reaction of a chromium compound such as chromium trioxide with amines or phosphoric amides is desirably carried out at a mol ratio of the chromium compound to the amines or the phosphoric amides of 1:0.1 through 1:10 at a temperature of 10° through 100° C., desirably 20° through 80° C., for several minutes through 20 hours, desirably 10 minutes through 5 hours. The use of too small an amount of the chromium compound results in only a small amount of the reaction product. Contrary to this, the use of too large an amount of the chromium compound results in an increase in the amount of the unreacted chromium compound.
The hydrocarbyloxy compounds of titanium, vanadium, hafnium and zirconium will now be explained.
The hydrocarbyloxy compounds of titanium usable in the present invention are those having the general formula:
Ti(OR.sup.16).sub.l X.sub.4-l
wherein R16 is a hydrocarbon group having 1 through 20 carbon atoms, X is a halogen atom, and l is a number of 1 through 4 (i.e. 1≦l≦4). Examples of R16 groups are methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, phenyl, tolyl, and cyclohexyl. Desirably, l is 2≦l≦4, and more desirably, l is 3≦l≦4. In the case of l<4, X is desirably chlorine.
The hydrocarbyloxy compounds of zirconium usable in the present invention are those having the general formula:
Zr(OR.sup.16).sub.l X.sub.4-l
wherein R16, X, and l are the same as defined above. Desirably, l is 2≦l≦4, and more desirably, l is 3≦l≦4. In the case of l≦4, X is desirably chlorine. Examples of the desirable compounds are Zr(OC3 H7)4, Zr(OC4 H9)4, Zr(OC5 H11)4, Zr(OC6 H5)4, and Zr(OC4 H9)3 Cl.
The hydrocarbyloxy compounds of hafnium usable in the present invention are those having the general formula:
Hf(OR.sup.16).sub.l X.sub.4-l
wherein R16, and X are the same as defined above, and l is a number of 1 through 3 (i.e. 1≦l≦3).
The reaction of chromium compounds such as chromium trioxide with hydrocarbyloxy compounds of titanium, vanadium, zirconium, and hafnium can be carried out in the presence of an inert organic solvent. The presence of oxygen and water in the reaction medium is not desirable and, therefore, the contamination of the reaction medium with oxygen and water should be avoided. Furthermore, the exposure of the reaction medium to light also is not desirable. The unreacted chromium compounds are desirably removed from the reaction mixture. It appears that the reaction product contains compounds having the following structure: ##STR2##
The germanium compounds having the general formula R1 R2 R3 R4 Ge and usable in the present invention consist of two groups. In the case of the first group, R1, R2 and R3 in the general formula are each independently a hydrocarbon group having 1 through 10 carbon atoms, and R4 is a hydrogen atom, a halogen atom, --OH group, or --OGeR1 R2 R3 group, and in the second group, R1, R2, R3 and R4 in the general formula are each independently --OR5 wherein R5 is a hydrocarbon group having 1 through 10 carbon atoms or a halogen atom, provided that R1, R2, R3 and R4 are not all halogen atoms.
In the first group of the germanium compounds, R1, R2 and R3 in the general formula are independently a hydrocarbon group having 1 to 10 carbon atoms. Examples of such groups are: for example, aliphatic hydrocarbon groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, and decylgroups; and aromatic hydrocarbon groups such as phenyl and tolyl groups. The aromatic hydrocarbon groups are desirably used in the present invention. R4 in the general formula is a hydrogen atom, a halogen atom, --OH, or --OGeR1 R2 R3. The halogen atom includes Cl, Br, or I, desirably Br. In the case of R4 =--OH, compounds having aliphatic hydrocarbon groups such as R1, R2 and R3 are unstable and, therefore, compounds having aromatic hydrocarbon groups are desirable.
Examples of these compounds are trimethyl-germane, trimethylchlorogermane, trimethylbromogermane, trimethyliodogermane, bis-trimethylgermoxane, triethylgermane, triethylchlorogermane, triethylbromogermane, triethyliodogermane, bis-triethylgermoxane, tripropylgerman, tripropylchlorogermane, tripropylbromogermane, tripropyliodogermane, bis-tripropylgermoxane, tributylgermane, tributylchlorogermane, tributylbromogermane, tributyliodogermane, bis-tributylgermoxane, trihexylgerman, trihexylchlorogermane, trihexyl-bronogerman, trihexyliodogermane, bis-trihexylgermoxane, trioctylgermane, trioctylchlorogermane, trioctylbromogermane, trioctyliodogermane, bis-trioctylgermoxane, tridecylgermane, tridecylchlorogermane, tridecylbromogermane, tridecyliodogermane, bis-tridecylgermoxane, triphenylgermane, triphenylchlorogermane, triphenylbromogermane, triphenyliodogermane, triphenylgermanol, bis-triphenylgermoxane, tritolylgermane, tritolylchlorogermane, tritolylbromogermane, tritolyliodogermane, tritolylgermanol, and bis-tritolylgermoxane.
In the second group of germanium compounds, R1, R2, R3 and R4 in the general formula are independently --OR5 or a halogen atom wherein R5 is a hydrocarbon group having 1 to 10 carbon atoms. Examples of R5 are methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, phenyl, tolyl, and cyclohexyl. The halogen atom is chlorine, bromine, or iodide, desirably chlorine. The number of the halogen atoms per germanium atom is 0 through 3, desirably 0 through 2 and more desirably 0 through 1. Accordingly, especially desirable compounds are represented by the general formulae: (R5 O)3 GeCl and (R5 O)4 Ge.
The tin compounds usable in the present invention are those having the general formula R1 R2 R3 R6 Sn wherein R1, R2 and R3 are the same as defined above and R6 is halogen atom or a --OH group. The halogen atom includes Cl, Br, or I, desirably Cl or Br. Examples of such tin compounds are trimethylchlorotin, trimethylbromotin, trimethyliodotin, trimethyltin hydroxide, triethylchlorotin, triethylbromotin, triethyliodotin, triethyltin hydroxide, tripropylchlorotin, tripropylbromotin, tripropyliodotin, tripropyltin hydroxide, tributylchlorotin, tributylbromotin, tributyliodotin, tributyltin hydroxide, trihexylchlorotin, trihexylbromotin, trihexyliodotin, trihexyltin hydroxide, trioctylchlorotin, trioctylbromotin, trioctyliodotin, trioctyltin hydroxide, tridecylchlorotin, tridecylbromotin, tridecyliodotin, tridecyltin hydroxide, triphenylchlorotin, triphenylbromotin, triphenyliodotin, triphenyltin hydroxide, tritolylchlorotin, tritolylbromotin, and tritolyltin hydroxide.
The reaction of the first group of germanium compounds with the chromium compounds, is, for example, those of (1) a trialkylbromogermane or triarylbromogermane with silver chromate, (2) a bis-trialkylgermoxane or bis-triarylgermoxane with chromic acid, (3) a triarylgermanol with chromium trioxide, and a trialkylgermane or triarylgermane with chromic acid. Examples of the reaction medium are methylene chloride, chloroform, carbon tetrachloride, benzene, toluene, pentane, hexane, heptane, and cyclohexane.
The reaction of the first group of germanium compounds with the chromium compounds is desirably carried out at a mol ratio of the germanium compounds to the chromium compounds of 1:0.1 through 1:10 at a temperature of 10° through 100° C., desirably 20° through 80° C., for several minutes through 20 hours, desirably 10 minutes through 5 hours. The use of too small an amount of the chromium compounds results in only a small amount of the reaction product. Contrary to this, the use of too large an amount of the chromium compounds results in an increase in the amount of the unreacted chromium compounds. The presence of a small amount of water in the reaction medium can desirably accelerate the reaction. It is estimated from the literature (e.g. Z. Chem. 20, 31, 1980) that the compounds obtained from the above-mentioned reaction are germanium chromates having the general formula: ##STR3##
In the reaction of the second group of germanium compounds with the chromium compounds, chromium trioxide is most desirably used as a chromium compound. The reaction is desirably carried out in a reaction solvent such as, for example, methylene chloride, chloroform, carbon tetrachloride, benzene, toluene, pentane, hexane, heptane, and cyclohexane. The desirable mol ratio of the germanium compound to chromium trioxide in the reaction is 1:0.1 through 1:10. The use of a chromium compounds in an amount less than the above range results in only a small amount of the reaction product. Contrary to this, the use of a chromium compounds in an amount more than the above range results in an increase in the amount of the unreacted chromium compounds. The reaction is generally carried out at a temperature of 10° through 100° C., desirably 20° through 80° C., for a dozen or so minutes through 50 hours, desirably 30 minutes through 30 hours. It is estimated that the reaction product contains compounds having the following general formula: ##STR4##
Examples of the reaction of tin compounds having the general formula R1 R2 R3 R4 Sn with chromium compounds are (1) a trialkylhalogenotin or triarylhalogenotin with silver chromate and (2) a trialkyltin hydroxide or triaryltin hydroxide with chromium trioxide. The reaction solvents usable in the reaction of the germanium compounds with the chromium compounds can also be used in this reaction. The reaction mol ratio, the reaction temperature and the reaction time period in respect to this reaction are also substantially the same as in the case of the germanium compounds. It is also estimated from the known literature (e.g. Z. Chem. 20, 31, 1980) that the reaction product contains compounds having the general formula: ##STR5##
The above-mentioned reaction products can be supported on an inorganic oxide carrier such as silica in any conventional manner. For instance, the inorganic oxide carrier substance is impregnated with a solution of the above-mentioned reaction product, followed by either vaporization (or distillation) of the solvent or filtration of the solution. The former is preferred. Supporting is generally carried out at a temperature of -10° through 70° C., desirably 0° through 55° C. The chromium compounds are supported on the carrier in an amount of 0.01 through 10% by weight, desirably 0.05 through 5% by weight and more desirably 0.1 through 3% by weight.
The supported solid obtained above is calcined and activated. This activation is generally carried out in the presence of oxygen. It is especially important that the water content of the atmosphere be low when the supported solid is calcined. The water content of the atmosphere should be 20 ppm or less, desirably 10 ppm or less and more desirably 1 ppm or less. Calcination can be carried out under an inert gas atmosphere or under a reduced pressure. However, calcination is preferably carried out under an oxidizing atmosphere, such as air. Activation of the supported solid by calcination is carried out at a temperature of 300° through 900° C., desirably 500° through 800° C. The activation time is generally 0.5 through 10 hours; however, it depends upon the activation temperature.
The organometallic compound component (B) usable, together with the solid catalyst component (A), in the present invention will now be explained.
The organomagnesium compound component usable in the present invention includes hydrocarbon-soluble organomagnesium compounds having the general formula:
M.sub.α Mg.sub.β R.sup.7.sub.p R.sup.8.sub.q X.sub.r Y.sub.s
wherein M is an element selected from aluminum, boron, beryllium, zinc or lithium; R7 and R8 are the same or different hydrocarbon groups having 1 to 20 carbon atoms; X and Y are the same or different groups selected from OR9, OSiR10 R11 R12, NR13 R14, or SR15 wherein R9, R10, R11, R12, R13, and R14 are each independently a hydrogen atom or a hydrocarbon group and R15 is a hydrocarbon group having 1 to 20 carbon atoms; α is zero or greater than 0, β is greater than zero, and p, q, r, and s are each zero or greater than zero, but p and q are not simultaneously zero, and p+q+r+s=mα+2β wherein m has a valency of M.
In the above-mentioned general formula, examples of the hydrocarbon groups represented by R7 through R15 are alkyl groups, desirably having 1 to 20 carbon atoms, cycloalkyl groups, desirably having 3 to 10 carbon atoms, or aryl groups, desirably having 6 to 20 carbon atoms. Typical examples of such groups are methyl, ethyl, propyl, butyl, amyl, hexyl, decyl, cyclohexyl, and phenyl groups. Especially, R7 is desirably an alkyl group, R9 through R14 may be a hydrogen atom, and R9 is desirably a hydrogen atom.
In the case of α>0, aluminum, boron, zinc, beryllium and lithium are desirably used as the metal M since these metals readily form hydrocarbon-soluble organomagnesium complexes. The ratio of magnesium to the metallic atom M (i.e. β/α) is desirably 0.2 or more and more desirably 0.5 or more although there is no critical limitation of this ratio.
The relationship p+q+r+s=mα+2β shows the stoichiometry of the organomagnesium compound component. The relationship (r+s)/(α+β), which means a ratio of the total number of X and Y to the total number of metallic atoms, is generally 0≦(r+s)/(α+β)≦1.5, desirably 0≦(r+s)/(α+β)≦1.0 and more desirably 0≦(r+s)/(α+β)≦0.8.
The above-mentioned organomagnesium complex compounds usable in the present invention are synthesized by reacting an organomagnesium compound represented by the general formula R7 MgX or R7 2 Mg, wherein R7 is the same as defined above and X is a halogen, with an organometallic compound represented by MR8 m or MR8 m-1 H, wherein M, R8 and m are the same as defined above, at a temperature ranging from room temperature to 150° C. in an inert hydrocarbon solvent, such as hexane, heptane, cyclohexane, benzene, and toluene. Furthermore, the above-mentioned organomagnesium compounds can also be synthesized by the reaction of (i) MgX2 and MR8 m or MR8 m-1 H or (ii) R7 MgX or MgR7 2 and R8 n MXm-n wherein M, R7 and R8 are the same as defined above and n is a number of 0 through m.
In the case of α=0 and γ=0 in the above-mentioned general formula of the organomagnesium compounds, that is, the hydrocarbon-soluble organomagnesium compounds having the general formula MgR7 p R8 q, the following three groups are generally involved.
(a) At least one of R7 and R8 is a secondary or tertially alkyl group having 4 to 6 carbon atoms;
(b) R7 and R8 are alkyl groups having different carbon atoms; and
(c) At least one of R7 and R8 is a hydrocarbon group having 6 or more carbon atoms.
Of these three groups, the corresponding following three groups are desirable for use in the present invention:
(a') Both R7 and R8 are alkyl groups having 4 to 6 carbon atoms and at least one of R7 and R8 is a secondary or tertially alkyl group.
(b') R7 is an alkyl group having 2 or 3 carbon atoms and R8 is an alkyl group having 4 or more carbon atoms.
(c') Both R7 and R8 are alkyl groups having 6 or more carbon atoms.
Examples of these groups are as follows. The secondary alkyl groups or the tertially alkyl groups having 4 to 6 carbon atoms in the above-mentioned cases (a) and (a') include, for example, sec-C4 H9, tert-C4 H9, --CH(C2 H5)2, --C(C2 H5)(CH3)2, --CH(CH3)(C4 H9), --CH(C2 H5)(C3 H7), --(CH3)2 (C3 H7), and --C(CH3)(C2 H5)2. The desirable group is a secondary alkyl group, especially the sec--C4 H9 group.
The alkyl groups having 2 or 3 carbon atoms in the above-mentioned cases (b) and (b') include, for example, ethyl and propyl groups, desirably the ethyl group. The alkyl groups having 4 or more carbon atoms include, for example, butyl, amyl, hexyl and octyl groups, desirably the butyl and hexyl groups.
The hydrocarbon groups having 6 or more carbon atoms in the above-mentioned cases (c) and (c') include, for example, an alkyl group, such as hexyl, octyl, or decyl group, and a phenyl group, desirably a hexyl group.
Examples of the above-mentioned organomagnesium compounds are (sec--C4 H9)2 Mg, (tert--C4 H9)2 Mg, n--C4 H9 --Mg--C2 H5, n--C4 H9 --Mg--sec--C4 H9, n--C4 H9 --Mg--tert--C4 H9, n--C6 H13 --Mg--C2 H5, (n--C6 H13)2 Mg, (n--C8 H17)2 Mg, and (n--C10 H21)2 Mg.
Examples of X in the above-mentioned general formula are desirably OR9 and OSiR10 R11 R12 and most desirably OSiR10 R11 R12. The ratio of OR9 or OSiR10 R11 R12 to the metallic magnesium atom (i.e. r) is desirably 0.1 through 2 and more desirably 0.2 through 1.5.
The organoaluminum compound conponents usable in the present invention include, for example, components obtained by reacting and/or mixing trialkylaluminum compounds with carbinols and/or silanols or hydrosiloxy compounds.
Examples of the trialkylaluminum compounds are trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-iso-propylaluminum, tri-n-butylaluminum, tri-iso-butylaluminum, triamylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, tridodecylaluminum and isoprenylaluminum. These compounds can be used alone or in mixtures thereof.
The carbinols having 1 to 10 carbon atoms include, for example, methyl alcohol, ethyl alcohol, n-and iso-propyl alcohol, n-, iso-and tert-butyl alcohol, n-, iso-, sec-and tert-amyl alcohol, phenol, and cresol.
The reaction ratio of the carbinol to the trialkylaluminum is 0.1 through 2 moles, desirably 0.15 through 1.5 moles and most desirably 0.2 through 1.3 moles, based on 1 mol of trialkylaluminum.
Examples of the silanols usable in the present invention are trimethylsilanol, triethylsilanol, tripropylsilanol, tributylsilanol, and triphenylsilanol. Hydrozates of, for example chlorosilanes and polysilanols can also be used in the present invention.
Examples of the hydrosiloxy compounds usable in the present invention are as follows: ##STR6##
The reaction ratio of the silanols or hydrosiloxy compounds to the trialkylaluminum is 0.1 through 5 moles, desirably 0.1 through 2 moles and most desirably 0.2 through 1.5 moles, based on 1 mol of the trialkylaluminum.
The ratio of the organoaluminum component to the organomagnesium component is 0.05 through 50 moles, desirably 0.1 through 10 moles, based on 1 mol of the organomagnesium component.
The organomagnesium component and the organoaluminum component can be added to a polymerization mixture separately or in the form of a mixture obtained from previous mixing of the organomagnesium component and the organoaluminum component. Previous contact between the solid catalyst component and a small amount of the component (B) prior to its addition to the polymerization mixture provides a good result.
The ratio of the component (B) to the component (A) in terms of the metals (gr. atom) in the component (B)/CR (gr. atom) in the component (A) is generally 0.01 through 3000, desirably 0.1 through 100.
The catalyst according to the present invention is suitably used in the polymerization of ethylene or in the copolymerization of ethylene in which ethylene is a main constituent. Monomers usable in the copolymerization of ethylene are mono-olefins or diolefins having 3 to 12 carbon atoms. Examples of such monomers are propylene, butene-1, pentene-1, 3-methylbutene-1, hexene-1, 4-methylpentene-1, 3-ethylbutene-1, heptene-1, octene-1, decene-1, butadiene, isoprene, 1,4-hexadiene, 1,5-hexadiene, 1,7-octadiene, dicyclopentadiene, and ethylidene norbornene. One or two of these monomers can be used in the copolymerization of ethylene.
The density of the ethylene polymers or ethylene copolymers produced by using the present catalyst is approximately 0.91 through 0.97.
Polymerization can be carried out in any conventional manner, including suspension polymerization, bulk polymerization, solution polymerization, and gas phase polymerization.
The polymerization reaction can be generally carried out at a temperature ranging, for example, from room temperature to approximately 300° C. However, the polymerization conditions depend upon the polymerization pressure, the partial pressure of the moomer, and the kinds and concentrations of the catalyst components. Generally speaking, polymerization is carried out in a slurry state at a temperature ranging from room temperature through 100° C. and in a solution state at a temperature of 100° through 200° C. Polymerization is desirably carried out in a slurry state. Furthermore, polymerization may be carried out under a gas phase condition substantially in the absence of an inert organic solvent.
When the polymerization reaction is carried out in the presence of an inert organic solvent, hydrocarbon solvents are desirably used. Examples of such organic hydrocarbon solvents are: aliphatic saturated hydrocabons, such as butane, isobutane, pentane, hexane, heptane, octane, isooctane, decane, and purified kerosene; alicyclic saturated hydrocarbons, such as cyclopentane, cyclohexane, dimethylcyclopentane, and methylcyclohexane; and aromatic hydrocarbons, such as benzene, toluene, and xylene. Desirable hydrocarbon solvents are isobutane, pentane, hexane, heptane, and cyclohexane.
Polymerization may be carried out in the presence of a molecular weight modifier, such as hydrogen, and halogenated hydrocarbons, desirably hydrogen. The amount of the molecular weight modifier can be optionally controlled as required.
Polymerization can be carried out by means of a conventional one-stage polymerization method using one reaction zone or by means of a so-called multi-stage polymerization method using a plurality of reaction zones. The polymers obtained by using the present catalyst have a wide molecular weight distribution and a relatively high molecular weight, even when obtained by using a one-stage polymerization method, and, therefore, are especially suitable for use in blow molding and film molding. Polymers having an additionally wide molecular weight distribution can be produced by means of multi-stage polymerization in which two or more polymerization conditions are used.
The present invention will now be specifically illustrated by, but is by no means limited to, the Examples set forth below.
The term "catalyst efficiency" used in the Examples is defined by the amount of polymers produced in one hour based on 1 g of the solid catalyst. The physical properties in the Examples were determined as follows:
Fifteen ml of titanium tetra n-butoxide, 120 ml of carbon tetrachloride and 2 g of anhydrous chromium trioxide were charged into a flask. The mixture was heated to a refluxing temperature of the solvent under stirring in a nitrogen atmosphere and allowed to react under reflux for 24 hours. Thus, a green reaction mixture was obtained. After removing solid matters from the reaction mixture by filtration, a reaction product solution was recovered.
One hundred grams of a commercially available silica (Davison 952® manufactured by W. R. Grace & Co., Davison Chemical Division) was added to the above-prepared solution of the titanium reaction product (corresponding to 1 g of chromium metal atom), together with 1 liter of n-hexane. The mixture was allowed to react at a temperature of 60° C. for 4 hours under stirring. The solvent was distrilled off and the resultant product was dried for further 2 hours under a reduced pressure. The resultant solid was calcined in a dried air at a temperature of 800° C. for 4 hours. This, a solid catalyst component was obtained.
13.8 g of di-n-butylmagnesium and 1.9 g of triethylaluminum were charged, together with 100 ml of n-heptane, into a flask purged with nitrogen and reacted at a temperature of 80° C. for 2 hours. Thus, an organomagnesium complex solution was obtained. As result of analysis, the composition of the complex was AlMg6.0 (C2 H5)3.0 (n-C4 H9)11.9 and the concentration of the organometal was 1.18 mol/l.
22.8 g of triethylaluminum, 430 ml of n-pentane and 12 g of hydromethylsiloxane tetramer were charged into a pressure resistant vessel and reacted at a temperature of 120° C. for 5 hours. The reaction product thus obtained was weighed out and the concentration of aluminum and the concentration of ethane after decomposition were determined. The composition of the reaction product was Al(C2 H5)2 (OSiH.CH3.C2 H5).
Fifty mg of the solid catalyst component obtained in (2) above, 0.05 m mol of the organomagnesium component obtained in (3) above and 0.15 m mol of the organoaluminum obtained in (4) above were charged, together with 1.6 liter of hexane, into an autoclave, which had been dried in vacuo and purged with nitrogen. Ethylene was added in an amount corresponding to a pressure of 10 kg/cm2 and hydrogen was added in such an amount that the total pressure becomes 14 kg/cm2, while the inside temperature of the autoclave was maintained at 80° C. The polymerization was carried out for 2 hours, while the total inside pressure of the autoclave was maintained at 14 kg/cm2 by supplying ethylene. Thus, 270 g of polyethylene was obtained.
The catalyst efficiency was 2700 g-polyethylene (PE)/ g-solid catalyst hr, MI of the polymer was 0.1 g/10 min and FR was 255.
The swelling ratio, which represents one characteristics of melt flowability, was determined. As a result, the swelling ratio of the resultant polymer was 0.81, which was remarkably smaller than that (i.e. 1.05) of a polymer obtained from a Phillips catalyst in which no titanium compound was contained in the above-prepared catalyst.
Example 1 was repeated, except that an organoaluminum compound obtained in the following manner was used in lieu of the organoaluminum compound synthesized in Example 1.
One hundred and twenty five m moles of triethylaluminum, 200 ml of n-pentane and 125 m moles, in terms of Si, of methylhydropolysiloxane having a viscosity of 50 centistokes were allowed to react at a temperature of 80° C. for 2 hours. As a result of analysis, it was confirmed that the composition of the reaction product was Al(C2 H5)2 (OSiHCH3 C2 H5).
The results of the polymerization were as follows.
Yield of polyethylene: 254 g
Catalyst efficiency: 2540 g-PE/g-solid catalyst.hr
MI: 0.09 g/10 min
FR: 220
One hundred grams of a commercially available silica (i.e. Davison 952®) was mixed with the solution of the titanium reaction product obtained in step (1) of Example 1 (in an amount corresponding to 1 g of chromium metal atom) and 500 ml of n-hexane and the mixture was allowed to react at a temperature of 60° C. for 4 hours under stirring. The solid matters were filtered out and dried in a dried air stream. The dried solid was calcined at a temperature of 800° C. for 4 hours in a dried air. Thus, a solid catalyst component was obtained.
Ethylene was polymerized in the same manner as in Example 1, except that the above-prepared solid catalyst component was used.
The results of the polymerization were as follows.
Yield of polyethylene: 240 g
Catalyst efficiency: 2400 g-PE/g-solid catalyst.hr
MI: 0.46 g/10 min
FR: 147
To 100 mg of the solid catalyst component obtained in Example 1, 0.01 m mol of an orgianomagnesium component Mg6.0 (n-C4 H9)12 (C2 H5)3.0 (a 1 mol/l solution in hexane) and 0.01 m mol of an organoaluminium compound Al(C2 H5)2 (OSiH.CH3.C2 H5) (a 1 mol/l solution in hexane) was added and the mixture was allowed to react at a room temperature for 1 day. The polymerization of ethylene in Example 1 was repeated except that the catalyst prepared above was used in lieu of the catalyst of Example 1.
The results of the polymerization were as follows.
Yield of polyethylene: 308 g
Catalyst efficiency: 3080 g-PE/g-solid catalyst.hr
MI: 0.06 g/10 min
FR:290
Ethylene was polymerized in the same manner as in Example 1 except that an organomagnesium component and an organoaluminum compound were changed as shown in Table 1.
The results are shown in Table 1.
TABLE 1
__________________________________________________________________________
Catalyst
Organomagnesium component Organoaluminum compound
efficiency
Amount Amount
g-PE/
MI
Example used used g-solid
g/
No. Composition m mol
Composition m mol
cat ·
10-min
__________________________________________________________________________
5 AlMg(n-C.sub.4 H.sub.9).sub.2 (C.sub.2 H.sub.5).sub.3
0.1 Al(C.sub.2 H.sub.5).sub.2 (OSiHCH.sub.3
C.sub.2 H.sub.5)
0.10 3000 0.04
6 AlMg.sub.3.0 (n-C.sub.4 H.sub.9).sub.4.0 (C.sub.2 H.sub.5).sub.2.0
(OSiHCH.sub.3 C.sub.4 H.sub.9).sub.3.0
0.1 Al(C.sub.2 H.sub.3).sub.2 (OSiHCH.sub.3
C.sub.2 H.sub.5)
0.15 2760 0.11
7 BMg(C.sub.2 H.sub.5).sub.2.8 (n-C.sub.4 H.sub.9).sub.2.2
" " 0.20 2510 0.14
8 BeMg.sub.4.0 (C.sub.2 H.sub.5).sub.3.1 (n-C.sub.4 H.sub.9).sub.6.8
" " " 2220 0.13
9 ZnMg.sub.2.0 (C.sub.2 H.sub.5).sub.2.1 (n-C.sub.4 H.sub.9).sub.3.9
" Al(i-C.sub. 4 H.sub.9).sub.2.5 (OSiHCH.su
b.3 C.sub.4 H.sub.9).sub.0.5
0.15 2800 0.12
10 Li.sub.2 Mg(i-C.sub.3 H.sub.7).sub.2 (n-C.sub.4 H.sub.9).sub.2
" Al(C.sub.3 H.sub.7).sub.2 (OSiHCH.sub.3
C.sub.3 H.sub.7)
" 2580 0.14
11 AlMg.sub.3.0 (nC.sub.4 H.sub.9).sub.4.5 (C.sub.2 H.sub.5)(OSiHCH.sub.
3 C.sub.2 H.sub.5).sub.1.5
0.2 -- -- 2740 0.41
12 Mg(sec-C.sub.4 H.sub.9).sub.0.8 (n-C.sub.4 H.sub.9).sub.0.8 (OSiHCH.s
ub.3 C.sub.4 H.sub.9).sub.0.4
0.1 Al(C.sub.2 H.sub.3).sub.2.0 (OC.sub.2
H.sub.5) 0.15 2920 0.68
13 (sec-C.sub.4 H.sub.9).sub.1.5 Mg(On-C.sub.4 H.sub.9).sub.0.5
0.05
Al(C.sub.2 H.sub.5).sub.2 (OSiHCH.sub.3
C.sub.2 H.sub.5)
" 2440 0.21
14 (sec-C.sub.4 H.sub.9).sub.0.8 Mg(n-C.sub.4 H.sub.9).sub.0.8 (On-C.sub
.4 H.sub.9).sub.0.4 " Al(C.sub.2 H.sub.5).sub.1.5 (OSiHCH.sub.3
C.sub.2 H.sub.5).sub.1.5
" 2300 0.24
__________________________________________________________________________
Ethylene was polymerized in the same manner as in Example 1 except that the compounds listed in Table 2 below were used. The results are also shown in Table 2.
TABLE 2
__________________________________________________________________________
Supported Cr amount
Calcining
Example (% by weight in
conditions
Catalyst efficiency
MI
No. Titanium compound
terms of Cr)
Temperature
Time
g-PE/g-solid cat · hr
(g/10-min)
FR
__________________________________________________________________________
15 Ti(Oi-Pr).sub.4
1 700 4 2580 0.1 220
16
##STR7## 0.5 600 4 2000 0.04 265
17 Ti(Oi-Bu).sub.4
1 800 3 2660 0.1 215
18 Ti(O2EthylHexyl).sub.4
0.5 750 3 1940 0.06 273
19 Zr(On-Bu).sub.4
0.7 700 4 2260 0.12 244
20 VO(On-Bu).sub.3
0.6 580 4 1740 0.11 255
21 Hf(OBu).sub.4
0.8 630 4 1650 0.08 241
__________________________________________________________________________
Ethylene was polymerized in the same manner as in Example 1 except that the components (B) listed in Table 3 were used. The solid catalyst component was prepared in the same manner as in Example 1.
The results are shown in Table 3.
TABLE 3
__________________________________________________________________________
Ex-
Component B
am- Amount Amount
ple
Organomagnesium
used used Catalyst efficiency
MI
No.
component m mol
Second component m mol
g-PE/g-solid ·
9/10-min
FR
__________________________________________________________________________
22 AlMg(n-C.sub.4 H.sub.9).sub.2 (C.sub.2 H.sub.5).sub.3
0.05 B(C.sub.2 H.sub.5).sub.3
0.15 3200 0.05 180
23 " " Al(C.sub.2 H.sub.5).sub.2.25 (C.sub.2 H.sub.5).sub.0.
5 (OSiHCH.sub.3 C.sub.2 H.sub.5).sub.0.25
0.15 3060 0.15 195
24 AlMg(n-C.sub.4 H.sub.9).sub.2 (C.sub.2 H.sub.5).sub.3
0.10 Zn(C.sub.2 H.sub.5).sub.2
0.10 2880 0.21 200
25 AlMg.sub.3.0 (n-C.sub.4 H.sub.9).sub.6 (C.sub.2 H.sub.5).sub.3
0.10 (n-C.sub.4 H.sub.9)Li
0.10 2900 0.14 210
__________________________________________________________________________
Thirty ml of CH2 Cl2, 5 m mol of hexaphenyldigermoxane, 5 m mol of chromium trioxide, and 5 m mol of H2 O were charged into a 100 ml flask purged with nitrogen. The mixture was stirred at a room temperature for 2 hours. Thus, a blown solution was obtained after removing a water layer. The solution thus obtained was dehydrated with MgSO4 and filtered. The chromium content of the solution was 3.4 mg-Cr atom/ml.
Silica (Davison 952®) was dried at a temperature of 800° C. for 4 hours in a dry nitrogen stream. 5 g of the dried silica was charged, together with 20 ml of CH2 Cl2, into a 100 ml flask purged with nitrogen. 14.6 ml of the solution obtained in (1) above was dropwise added to the flask at a room temperature under stirring. After stirring for 30 minutes, CH2 Cl2 was distilled off under a reduced pressure. The resultant solid was calcined at a temperature of 800° C. for 4 hours in a dry air fluidized state. Thus, the solid catalyst component was obtained.
13.6 g of di-n-butylmagnesium and 1.83 g of triethylaluminum were charged, together with 100 ml of n-heptane, into a flask purged with nitrogen and reacted at a temperature of 80° C. for 2 hours. Thus, an organomagnesium complex solution was obtained. As a result of analysis, the composition of the complex was AlMg6.0 (C2 H5)3.0 (n-C4 H9)11.9 and the concentration of the organometal was 1.18 mol/l.
22.9 g of triethylaluminum, 430 ml of n-pentane and 12.05 g of hydromethylsiloxane tetramer were charged into a pressure resistant vessel and reacted at a temperature of 120° C. for 5 hours. The reaction product thus obtained was weighed out and the concentration of aluminum and the concentration of ethane after decomposition were determined. The composition of the reaction product was Al(C2 H5)2 (OSiH.CH3.C2 H5).
Fifty mg of the solid catalyst component obtained in (2) above, 0.05 m mol of the organomagnesium component obtained in (3) above and 0.15 m mol of the organoaluminum obtained in (4) above (Mg+Al=0.20 m mol) were charged, together with 0.8 liter of hexane, into an autoclave, which had been dried in vacuo and purged with nitrogen. Ethylene was added in an amount corresponding to a pressure of 10 kg/cm2 and hydrogen was added in such an amount that the total pressure becomes 14 kg/cm2, while the inside temperature of the autoclave was maintained at 80° C. The polymerization was carried out for 2 hours, while the total inside pressure of the autoclave was maintained at 14 kg/cm2 by supplying ethylene. Thus, 280 g of polymer was obtained.
The catalyst activity was 560,000 g/g. Cr atom, MI 0.34 g/10 min., FR 90 and the bulk density 0.42 g/c.c.
Ethylene was polymerized in the same manner as in Example 26 except that the organomagnesium components and the organoaluminum components listed in Table 4 below were used. The results are shown in Table 4.
Thirty ml of CH2 Cl2, 5 m moles of trigermane, 5 m moles of chromium trioxide and 5 m moles of H2 O were charged into a 100 ml flask purged with nitrogen. The mixture was stirred at a room temperature for 2 hours. Thus, a blown solution was obtained after removing a water layer. The solution thus obtained was dehydrated with MgSO4 and filtered. The chromium content of the solution was 3.7 mg Cr--atom/ml. The solution was supported on the carrier and calcined in the same manner as in Example 27.
Thus, the solid catalyst component was obtained.
Ethylene was polymerized in the same manner as in Example 26 except that the above-prepared solid catalyst was used. The results are shown in Table 4 below.
Thirty ml of CH2 Cl2, 5 m mol of triphenyltin hydroxide, and 5 m moles of H2 O were charged into a 100 ml flask purged with nitrogen. The mixture was stirred at a room temperature for 3 hours. A blown solution was obtained after filtration. The chromium content of the solution was 4.2 mg Cr atom/ml. The solution was supported on the carrier and calcined in the same manner as in Example 26. Thus, the solid catalyst component was obtained.
Ethylene was polymerized in the same manner as in Example 26 except that the above-prepared solid catalyst was used. The results are shown in Table 4.
Thirty ml of carbon tetrachloride, 5 m moles of tetra-n-butoxygermanium, and 5 m moles of chromium trioxide were charged into a 100 ml flask purged with nitrogen and allowed to react for 15 hours under reflux. After filtration, a black-greenish brown solution was obtained. The chromium content of the solution was 0.32 mg Cr atom/ml. The solution was supported on the carrier and calcined in the same manner as in Example 26.
Ethylene was polymerized in the same manner as in Example 26 except that the above-prepared solid catalyst was used. The results are shown in Table 4.
Ethylene was polymerized in the same manner as in Example 26 except that the solid catalyst component of Example 34 as well as the organomagnesium component and the organoaluminum component listed in Table 4 were used. The results are shown in Table 4.
TABLE 4
__________________________________________________________________________
Starting materils for A- A-
Ex-
solid catalyst component
mount mount
Catalyst activity
am- Cr used used
(g/g · Cr)
MI
ple No.
Ge or Sn compound
com- pound
Other
Organoaluminum component
(m mol)
Organomagnesium component
(m mol)
##STR8## (g/ 10-min)
FR
__________________________________________________________________________
26 (φ.sub.3 Ge).sub.2 O
CrO.sub.3
H.sub.2 O
AlEt.sub.2.0 (OSiHMeEt)
0.15
AlMg.sub.6.0 Et.sub.3.0 nBu.sub.11.9
0.05
560,000 0.34
90
[2800]
27 " " " -- -- AlMgnBu.sub.2.0 Et.sub.3.0
0.20
604,000 0.07
130
[3020]
28 " " " AlEt.sub.2.0 (OSiHMeEt)
0.20
BMgEt.sub.2.8 nBu.sub.2.2
0.10
440,000 0.21
110
[2200]
29 " " " " " BeMgEt.sub.2.1 nBu.sub.2.9
" 470,000 0.18
105
[2350]
30 " " " " " ZnMg.sub.2.0 Et.sub.2.1 nBu.sub.3.9
" 492,000 0.19
110
[2460]
31 " " " AliPr.sub.2 (OSiHMeiPr)
" Li.sub.2 MgiPr.sub.2 nBu.sub.2
" 476,000 0.20
103
[2380]
32 Me.sub.3 GeH
CrO.sub.3
H.sub.2 O
AlEt.sub.2.0 (OSiHMeEt)
0.15
AlMg.sub.6.0 Et.sub.3.0 nBu.sub.11.9
0.05
530,000 0.18
120
[2650]
33 φ.sub.3 SnOH
CrO.sub.3
-- " " " " 580,000 0.66
80
[2900]
34 (nBuO).sub.4 Ge
CrO.sub.3
-- " " " " 410,000 0.21
115
[2100]
35 " " H.sub.2 O
AlEt.sub.2.0 (OSiHMeEt)
" AlMg.sub.6.0 Et.sub.1.5 nBu.sub.12.0
" 470,000 0.20
117
(OSiHMeEt).sub.1.5
[2350]
__________________________________________________________________________
Twenty ml of CH2 Cl2, and 0.5 g (5 m moles) of chromium trioxide were charged into a 100 ml flask purged with nitrogen and 1.2 ml (5 m moles) of (n--C4 H9)3 N was dropwise added to the mixture at a room temperature under stirring. The mixture was stirred for further 2 hours and, after removing the unreacted solid by filtration, a blackish blown solution was obtained. The chromium content in the solution was 3.6 mg Cr atom/ml.
Five grams of silica (Davison 952®), which was previously dried at a temperature of 800° C. for 4 hours in a dry nitrogen stream, was charged into a 100 ml flask purged with nitrogen and, then, 20 ml of CH2 Cl2 was added thereto. 4.1 ml of the solution prepared in (1) above was dropwise added to the mixture at a room temperature under stirring. After stirring for further 30 minutes, CH2 Cl2 was distilled off under a reduced pressure. Thus, pale blown solid was obtained.
The solid obtained in (2) above was calcined at a temperature of 800° C. for 4 hours in a dry air fluidized state. Thus, a solid catalyst component was obtained.
13.8 g of di-n-butylmagnesium and 6.81 g of Al(C2 H5)1.50 (OSi.H.CH3.C2 H5)1.50 were charged, together with 100 ml of n-heptane, into a 500 ml flask purged with nitrogen and reacted at a temperature of 80° C. for 2 hours. Thus, a siloxy-containing organomagnesium complex having a composition of AlMg3.0 (C2 H5)1.50 (n-C4 H9)6.0 (OSi.H.CH3.C2 H5)1.50 was obtained.
Forty mg of the solid catalyst component obtained in (3) above, and 0.20 m mol [Mg+Al=0.20 m mol] of the siloxy-containing organomagnesium component obtained in (4) above were charged, together with 0.8 l of dehydrated and deaerated hexane, into a 1.5 liter autoclave, which has been evacuated in vacuo and purged with nitrogen. Ethylene was added in an amount corresponding to a pressure of 10 kg/cm2 and hydrogen was added in such an amount that the total pressures becomes 14 kg/cm2, while the inside temperature of the autoclave was maintained at 80° C. The polymerization was carried out for 2 hours, while the total inside pressure of the autoclave was maintained at 14 kg/cm2 by supplying ethylene. Thus, 176 g of polymer was obtained.
The catalyst activity was 629,000 g/g.Cr atom, MI 0.23 g/10 min and FR 140. The particle size distribution of the polymer was such that 20 mesh up was 21%, 28 mesh up 39%, and 35 mesh up 21%. Thus, the resultant polymer had a large particle size, more than 80% of which particles was a size not passing through a 35 mesh sieve.
Ethylene was polymerized in the same manner as in Example 36 except that the compounds listed in Table 5 was used in lieu of the amine compound of Example 36 and the amount of the chromium supported was changed. The results are shown in Table 5 below.
Ethylene was polymerized in the same manner as in Example 37 except that the amount and the composition of the organomagnesium component were changed. The results are shown in Table 5.
13.80 g of di-n-butylmagnesium and 1.10 g of triethylaluminum were charged, together with 200 ml of n-heptane, into a 500 ml flask and allowed to react at a temperature of 80° C. for 2 hours under stirring. Thus, an organomagnesium component having a composition of AlMg6 (C2 H5)3 (n--C4 H9)12 was prepared.
Ethylene was polymerized in the same manner as in Example 36 except that the organomagnesium component obtained above was used. The results are shown in Table 5.
13.80 g of di-n-butylmagnesium and 2.85 g of triethylaluminum were charged, together with 200 ml of n-heptane, into a 500 ml flask and allowed to react at a temperature of 80° C. for 2 hours under stirring. Thus, an organomagnesium having a composition of AlMg4 (C2 H5)3 (n-C4 H9)8 was obtained. The solution thus obtained was cooled to a temperature of 10° C. and 50 ml of a n-heptane solution containing 50 m mol of n-butanol was dropwise added to the solution over 1 hour, while the reaction mixture was cooled. Thus, an alkoxy-containing organomagnesium component having a composition of AlMg4.0 (C2 H5)2.70 (n--C4 H9)6.3 (O--n-Bu)2.0 was obtained.
Ethylene was polymerized in the same manner as in Example 36 except that the organomagnesium compound obtained above was used. The results are shown in Table 5 below.
Ethylene was polymerized in the same manner as in Example 36 except that organometallic compound components listed in Table 5 were used. The results are shown in Table 5.
TABLE 5
__________________________________________________________________________
Catalyst activity
Starting material
Amount of Amont
(g/g · Cr)
Example No.
for chromium compound component
Cr supported (wt %)
Organometallic component
used (m mol)
##STR9## MI (g/10-min)
FR
__________________________________________________________________________
36 nBu.sub.3 N
0.7 AlMg.sub.3.0 Et.sub.1.5 nBu.sub.6.0
0.20 629,000 0.23 140
(OSiHMeEt).sub.1.5 [2200]
37 iBu.sub.2 NH
0.7 " " 574,000 0.20 145
[2020]
38 nHexNH.sub.2
1.0 " " 400,000 0.22 148
[2000]
39
##STR10## 1.0 " " 324,000 [1620]
0.52 120
40 (Me.sub.2 N).sub.3 PO
0.7 " " 509,000 0.30 123
[1780]
41 nBu.sub.3 N
" " 0.10 571,000 0.17 150
[2000]
42 " " AlMg.sub.6.0 Et.sub.1.0 nBu.sub.12.0
0.20 600,000 0.21 145
(OSiHMeEt).sub.2.0 [2100]
43 " " AlMg.sub.6.0 Et.sub.3.0 nBu.sub.12.0
" 474,000 0.01 --
[1660]
44 nBu.sub.3 N
0.7 AlMg.sub.4.0 Et.sub.2.7 nBu.sub.6.3 (ONBu).sub.2.0
0.20 537,000 0.16 147
[1880]/ -45 " " AlEt.sub.2.0
(OSiHMeEt).su
b.1.0 " 451,00
0 0.90 90
[1580]
46 nBu.sub.3 N
" iBuMgnBu " 432,000 0.01 --
[1510]
47 " " BMgEt.sub.2.8 nBu.sub.2.2
" 438,000 0.02 --
[1530]
48 " " BeMgEt.sub.2.1 nBu.sub.2.9
" 442,000 0.01 --
[1550]
49 " " ZnMg.sub.2.0 Et.sub.2.1 nBu.sub.3.9
" 455,000 0.01 --
[1590]
50 " " Li.sub.2 MgiPr.sub.2 nBu.sub.2
" 463,000 0.03 --
[1620]
51 " " nBuLi " 512,000 0.005 --
[1790]
52 " " Et.sub.2 Zn 0.40 287,000 0.15 150
[1000]
__________________________________________________________________________
Claims (22)
1. A catalyst for polymerizing olefins comprising:
(A) a solid catalyst component obtained by calcining a product produced by reacting (a) at least one compound selected from an amine compound, a phosphoric acid amide, a hydrocarbyloxy compound of titanium, vanadium, hafnium or zirconium, and a germanium compound having the general formula:
R.sup.1 R.sup.2 R.sup.3 R.sup.4 Ge
wherein (i) R1, R2 and R3 are each independently a hydrocarbon group having 1 through 10 carbon atoms, and R4 is a hydrogen atom, a halogen atom, a --OH group, or a --OGeR1 R2 R3 group or (ii) R1, R2, R3 and R4 are each independently --OR5 wherein R5 is a hydrocarbon group having 1 through 10 carbon atoms, or a halogen atom, and a tin compound having the general formula:
R.sup.1 R.sup.2 R.sup.3 R.sup.6 Sn
wherein R1, R2 and R3 are the same as defined above and R6 is a halogen atom, or a --OH group, with (b) at least one chromium compound (I) in the absence of a carrier and then supporting the reaction product on an inorganic oxide carrier, or (II) effecting the reaction in the presence of an inorganic oxide whereby the product forms on the carrier; and,
(B) an organometallic compound component selected from the following groups (1) through (5):
(1) a hydrocarbon-soluble organomagnesium component having the general formula:
M.sub.α Mg.sub.β R.sup.7.sub.p R.sup.8.sub.q X.sub.r Y.sub.s
wherein M is an element selected from aluminum, boron, beryllium, zinc and lithium; R7 and R8 are the same or different hydrocarbon groups having 1 to 20 carbon atoms; X and Y are the same or different groups selected from OR9, OSiR10 R11 R12, NR13 R14, or SR15 wherein R9, R10, R11, R12, R13, and R14 are each independently a hydrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms, and R15 is a hydrocarbon group having 1 to 20 carbon atoms; α is zero or greater than zero, β is greater than zero and p, q, r, and s are each zero or greater than zero and both p and q are not zero at the same time and have the relationship p+q+r+s=mα+2β wherein m has a valency of M;
(2) an organoaluminum component obtained by reacting (i) one mole of a trialkylaluminum compound with (ii) 0.1 to 2 moles of a carbinol having 1 to 10 carbon atoms, 0.1 to 5 moles of a silanol or siloxane, or a mixture thereof;
(3) a component comprising said hydrocarbon-soluble organomagnesium component (1) and said organoaluminum component (2);
(4) a component comprising said hydrocarbon-soluble organomagnesium component (1) and an organoboron, organozinc, or organolithium compound; and
(5) a component comprising said organo-aluminum component (2) and an organoboron, organozinc, or organolithium compound.
2. A catalyst as claimed in claim 1 wherein the inorganic oxide carrier is silica or silica-alumina.
3. A catalyst as claimed in claim 1 or 2 wherein the inorganic oxide carrier has a surface area of 300 m2 /g or more and a specific pore volume of 1 ml/g or more.
4. A catalyst as claimed in claim 1 or 2 wherein the reaction product of the component (A) is that obtained by the reaction of an aliphatic amine and chromium trioxide.
5. A catalyst as claimed in claim 1 or 2 wherein the reaction product of the component (A) is that obtained by the reaction of an aliphatic phosphoric acid triamide compound and chromium trioxide.
6. A catalyst as claimed in claim 1 or 2 wherein the reaction product of the component (A) is that obtained by the reaction of a hydrocarbyloxy compound of titanium, vanadium, hafnium and zirconium and chromium trioxide.
7. A catalyst as claimed in claim 1 or 2 wherein the reaction product of the component (A) is that obtained by the reaction of a germanium compound with chromium trioxide.
8. A catalyst as claimed in claim 1 or 2 wherein the reaction product of the component (A) is that obtained by the reaction of a tin compound with chromium trioxide.
9. A catalyst as claimed in claim 1 or 2 wherein the content of chromium in the solid catalyst component is 0.01 through 5% by weight in terms of the chromium atom.
10. A catalyst as claimed in claim 1 or 2 wherein α and β in the general formula of the organomagnesium compound are α>0 and β/α≧0.2.
11. A catalyst as claimed in claim 1 or 2 wherein α and β in the general formula of the organomagnesium compound are α<0 and β/α≧0.5.
12. A catalyst as claimed in claim 1 or 2 wherein X and Y in the general formula of the organomagnesium component are each independently OR9 or OSiR10 R11 R12.
13. A catalyst as claimed in claim 1 or 2 wherein α,β, r and s in the general formula of the organomagnesium compound are 0≦(r+s)/(α+β)≦1.
14. A catalyst as claimed in claim 1 or 2 wherein α, β, r and s in the general formula of the organomagnesium compound are 0≦(r+s)/(α+β)≦0.8.
15. A catalyst as claimed in claim 1 or 2 wherein X in the general formula of the organomagnesium compound is an OSiR10 R11 R12 group wherein R10, R11, and R12 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
16. A catalyst as claimed in claim 1 or 2 wherein X in the general formula of the organomagnesium compound is an OSiR10 R11 R12 group wherein R10 is a hydrogen atom or R4, R5, R6 are each independently a hydrocarbon group having 1 to 7 carbon atoms.
17. A catalyst as claimed in claim 1 or 2 wherein X in the general formula of the organomagnesium compound is an OSiR10 R11 R12 group wherein R10 is a hydrogen atom and R11 and R12 are each independently a hydrocarbon group selected from methyl, ethyl, propyl, butyl, amyl, hexyl, phenyl, or tolyl.
18. A catalyst as claimed in claim 1 or 2 wherein the organoaluminum compound (B) is that obtained by the reaction of 1 mol of trialkylaluminum with 0.1 through 2 moles of silanol or siloxane.
19. A catalyst as claimed in claim 1 or 2 wherein the organoaluminum compound is that obtained by the reaction of 1 mole of trialkylaluminum with 1.5 moles of carbinol.
20. A catalyst as claimed in claim 1 or 2 wherein the organometallic compound contains a Si-H linkage therein.
21. A catalyst as claimed in claim 1 or 2 wherein the organometallic compound contains 0.1 to 2 moles of a silicon group per 1 gram atom of the metal atom in the component (B).
22. A catalyst as claimed in claim 1 or 2 wherein the solid catalyst component (A) is brought into contact with a small amount of the component (B) prior to the usage thereof.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56-83828 | 1981-06-02 | ||
| JP8382881A JPS57198708A (en) | 1981-06-02 | 1981-06-02 | Catalyst for polyolefin production |
| JP56-84308 | 1981-06-03 | ||
| JP8430881A JPS57200405A (en) | 1981-06-03 | 1981-06-03 | Catalyst for olefin polymerization |
| JP10130881A JPS585307A (en) | 1981-07-01 | 1981-07-01 | Catalyst for alpha-olefin polymerization |
| JP56-101308 | 1981-07-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4451573A true US4451573A (en) | 1984-05-29 |
Family
ID=27304346
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/385,221 Expired - Lifetime US4451573A (en) | 1981-06-02 | 1982-06-04 | Catalyst for polymerization of olefins |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US4451573A (en) |
| EP (1) | EP0067607B1 (en) |
| DE (1) | DE3275189D1 (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5451645A (en) * | 1989-08-10 | 1995-09-19 | Phillips Petroleum Company | Process for olefin polymerization |
| US5523507A (en) * | 1989-08-10 | 1996-06-04 | Phillips Petroleum Company | Process of trimerizing and oligomerizing olefins using chromium compounds |
| US5969058A (en) * | 1997-12-23 | 1999-10-19 | Ppg Industries Ohio, Inc. | Color-plus-clear composite coating composition containing tin catalysts |
| US6251999B1 (en) | 1997-12-23 | 2001-06-26 | Ppg Industries Ohio, Inc. | Tin carboxylate catalysts for epoxy-acid coating compositions |
| US20050187098A1 (en) * | 2004-02-20 | 2005-08-25 | Knudsen Ronald D. | Methods of preparation of an olefin oligomerization catalyst |
| US20050187391A1 (en) * | 2004-02-20 | 2005-08-25 | Knudsen Ronald D. | Methods of preparation of an olefin oligomerization catalyst |
| US20050187418A1 (en) * | 2004-02-19 | 2005-08-25 | Small Brooke L. | Olefin oligomerization |
| US20060183630A1 (en) * | 2003-02-26 | 2006-08-17 | Cann Kevin J | Production of broad molecular weight polyethylene |
| US20070043181A1 (en) * | 2005-08-19 | 2007-02-22 | Knudsen Ronald D | Methods of preparation of an olefin oligomerization catalyst |
| US20090163755A1 (en) * | 2007-12-21 | 2009-06-25 | Chevron Phillips Chemical Company Lp | Processes for Dimerizing or Isomerizing Olefins |
| US20090312506A1 (en) * | 2002-12-27 | 2009-12-17 | Univation Technologies, Llc. | Production of polyethylene |
| US20100022727A1 (en) * | 2008-07-23 | 2010-01-28 | Al-Arifi Abdullah Saad N | Polymer supported chrome catalyst for olefins polymerization |
| CN102388071A (en) * | 2009-04-10 | 2012-03-21 | 沙特基础工业公司 | Process for the production of an ethylene polymer using a chromium containing catalyst |
| US9550841B2 (en) | 2004-02-20 | 2017-01-24 | Chevron Phillips Chemical Company Lp | Methods of preparation of an olefin oligomerization catalyst |
| US9586872B2 (en) | 2011-12-30 | 2017-03-07 | Chevron Phillips Chemical Company Lp | Olefin oligomerization methods |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015153485A1 (en) | 2014-04-01 | 2015-10-08 | The Research Foundation For The State University Of New York | Electrode materials for group ii cation-based batteries |
| MX2019010509A (en) | 2017-03-06 | 2019-12-18 | Grace W R & Co | ELECTRON DONORS FOR THE PREPARATION OF THE ZIEGLER-NATTA PRE-CATALYST AND THE CATALYST SYSTEM FOR OLEFIN POLYMERIZATION. |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3635840A (en) * | 1969-03-17 | 1972-01-18 | Phillips Petroleum Co | Polymerization catalyst |
| US3876554A (en) * | 1973-11-08 | 1975-04-08 | Chemplex Co | Organotin chromate polymerization catalyst |
| US3884832A (en) * | 1974-02-04 | 1975-05-20 | Chemplex Co | Organotin chromate polymerization catalyst |
| US4041225A (en) * | 1975-12-29 | 1977-08-09 | Chemplex Company | Polymerization catalyst and method |
| US4368302A (en) * | 1979-03-28 | 1983-01-11 | Bp Chemicals Limited | Polymerization process and products therefrom |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL278927A (en) * | 1962-04-16 | |||
| BE632184A (en) * | 1962-05-11 | |||
| GB1061736A (en) * | 1963-03-07 | 1967-03-15 | Eastman Kodak Co | Process for the polymerization of -a-monoolefins |
| US3847957A (en) * | 1972-03-24 | 1974-11-12 | Standard Oil Co | Chromyl bis-(triorganotitanates)and related compounds |
| US3752795A (en) * | 1972-03-24 | 1973-08-14 | Standard Oil Co | Polymerization of olefins with a chomyl bis(triorganotitanate catalyst |
| US4020092A (en) * | 1973-11-08 | 1977-04-26 | Chemplex Company | Compounds bis(tributyltin)chromate and bis(triphenyltin)chromate |
| US3928304A (en) * | 1973-11-08 | 1975-12-23 | Chemplex Co | Method of making polyolefins using organotin chromate polymerization catalyst |
| US3985676A (en) * | 1974-01-24 | 1976-10-12 | National Petro Chemicals Corporation | Catalyst composition and method for the preparation thereof |
| GB2023153A (en) * | 1978-06-13 | 1979-12-28 | Bp Chem Int Ltd | Polymerisation of ethylene |
| US4204050A (en) * | 1978-11-09 | 1980-05-20 | The Dow Chemical Company | Polymerization of α-olefins with a dual transition metal catalyst |
| JPS57198705A (en) * | 1981-06-01 | 1982-12-06 | Asahi Chem Ind Co Ltd | Olefin polymerization catalyst |
-
1982
- 1982-06-01 DE DE8282302811T patent/DE3275189D1/en not_active Expired
- 1982-06-01 EP EP82302811A patent/EP0067607B1/en not_active Expired
- 1982-06-04 US US06/385,221 patent/US4451573A/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3635840A (en) * | 1969-03-17 | 1972-01-18 | Phillips Petroleum Co | Polymerization catalyst |
| US3876554A (en) * | 1973-11-08 | 1975-04-08 | Chemplex Co | Organotin chromate polymerization catalyst |
| US3884832A (en) * | 1974-02-04 | 1975-05-20 | Chemplex Co | Organotin chromate polymerization catalyst |
| US4041225A (en) * | 1975-12-29 | 1977-08-09 | Chemplex Company | Polymerization catalyst and method |
| US4368302A (en) * | 1979-03-28 | 1983-01-11 | Bp Chemicals Limited | Polymerization process and products therefrom |
Cited By (39)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5451645A (en) * | 1989-08-10 | 1995-09-19 | Phillips Petroleum Company | Process for olefin polymerization |
| US5523507A (en) * | 1989-08-10 | 1996-06-04 | Phillips Petroleum Company | Process of trimerizing and oligomerizing olefins using chromium compounds |
| US5763723A (en) * | 1989-08-10 | 1998-06-09 | Phillips Petroleum Company | Chromium compounds and uses thereof |
| US5786431A (en) * | 1989-08-10 | 1998-07-28 | Phillips Petroleum Company | Process for olefin polymerization |
| US5814575A (en) * | 1989-08-10 | 1998-09-29 | Phillips Petroleum Company | Chromium compounds and uses thereof |
| US5969058A (en) * | 1997-12-23 | 1999-10-19 | Ppg Industries Ohio, Inc. | Color-plus-clear composite coating composition containing tin catalysts |
| US6251999B1 (en) | 1997-12-23 | 2001-06-26 | Ppg Industries Ohio, Inc. | Tin carboxylate catalysts for epoxy-acid coating compositions |
| US8420754B2 (en) | 2002-12-27 | 2013-04-16 | Univation Technologies, Llc | Production of polyethylene |
| US20090312506A1 (en) * | 2002-12-27 | 2009-12-17 | Univation Technologies, Llc. | Production of polyethylene |
| US20110060111A1 (en) * | 2002-12-27 | 2011-03-10 | Univation Technologies, Llc | Production of Polyethylene |
| EP1596984A4 (en) * | 2003-02-26 | 2007-06-27 | Univation Tech Llc | Production of broad molecular weight polyethylene |
| US20060183630A1 (en) * | 2003-02-26 | 2006-08-17 | Cann Kevin J | Production of broad molecular weight polyethylene |
| US7326760B2 (en) * | 2003-02-26 | 2008-02-05 | Univation Technologies, Llc | Production of broad molecular weight polyethylene |
| US20080090976A1 (en) * | 2003-02-26 | 2008-04-17 | Univation Tehnologies, Llc | Production of broad molecular weight polyethylene |
| CN1753729B (en) * | 2003-02-26 | 2012-02-15 | 尤尼威蒂恩技术有限责任公司 | Production of broad molecular weight polyethylene |
| US8076262B2 (en) * | 2003-02-26 | 2011-12-13 | Univation Technologies, Llc | Production of broad molecular weight polyethylene |
| US20090270567A1 (en) * | 2004-02-19 | 2009-10-29 | Chevron Phillips Chemical Company Lp | Olefin Oligomerization |
| US20050187418A1 (en) * | 2004-02-19 | 2005-08-25 | Small Brooke L. | Olefin oligomerization |
| US7994376B2 (en) | 2004-02-19 | 2011-08-09 | Chevron Phillips Chemical Company Lp | Olefin oligomerization |
| US20050187098A1 (en) * | 2004-02-20 | 2005-08-25 | Knudsen Ronald D. | Methods of preparation of an olefin oligomerization catalyst |
| US8993822B2 (en) | 2004-02-20 | 2015-03-31 | Chevron Phillips Chemical Company Lp | Methods of preparation of an olefin oligomerization catalyst |
| US20080177122A1 (en) * | 2004-02-20 | 2008-07-24 | Chevron Phillips Chemical Company Lp | Methods of Preparation of an Olefin Oligomerization Catalyst |
| US8329608B2 (en) | 2004-02-20 | 2012-12-11 | Chevron Phillips Chemical Company Lp | Methods of preparation of an olefin oligomerization catalyst |
| US7820581B2 (en) | 2004-02-20 | 2010-10-26 | Chevron Phillips Chemical Company Lp | Methods of preparation of an olefin oligomerization catalyst |
| US20110021343A1 (en) * | 2004-02-20 | 2011-01-27 | Chevron Phillips Chemical Company Lp | Methods of Preparation of an Olefin Oligomerization Catalyst |
| US7384886B2 (en) | 2004-02-20 | 2008-06-10 | Chevron Phillips Chemical Company Lp | Methods of preparation of an olefin oligomerization catalyst |
| US20080058534A1 (en) * | 2004-02-20 | 2008-03-06 | Chevron Phillips Chemical Company Lp | Methods of Preparation of an Olefin Oligomerization Catalyst |
| US9550841B2 (en) | 2004-02-20 | 2017-01-24 | Chevron Phillips Chemical Company Lp | Methods of preparation of an olefin oligomerization catalyst |
| US20050187391A1 (en) * | 2004-02-20 | 2005-08-25 | Knudsen Ronald D. | Methods of preparation of an olefin oligomerization catalyst |
| US7910670B2 (en) | 2005-08-19 | 2011-03-22 | Chevron Phillips Chemical Company Lp | Methods of preparation of an olefin oligomerization catalyst |
| US20090292090A1 (en) * | 2005-08-19 | 2009-11-26 | Chevron Phillips Chemical Company Lp | Methods of Preparation of an Olefin Oligomerization Catalyst |
| US20070043181A1 (en) * | 2005-08-19 | 2007-02-22 | Knudsen Ronald D | Methods of preparation of an olefin oligomerization catalyst |
| US7902415B2 (en) | 2007-12-21 | 2011-03-08 | Chevron Phillips Chemical Company Lp | Processes for dimerizing or isomerizing olefins |
| US20090163755A1 (en) * | 2007-12-21 | 2009-06-25 | Chevron Phillips Chemical Company Lp | Processes for Dimerizing or Isomerizing Olefins |
| US8247342B2 (en) * | 2008-07-23 | 2012-08-21 | Al-Arifi Abdullah Saad N | Polymer supported chrome catalyst for olefins polymerization |
| US20100022727A1 (en) * | 2008-07-23 | 2010-01-28 | Al-Arifi Abdullah Saad N | Polymer supported chrome catalyst for olefins polymerization |
| CN102388071A (en) * | 2009-04-10 | 2012-03-21 | 沙特基础工业公司 | Process for the production of an ethylene polymer using a chromium containing catalyst |
| CN102388071B (en) * | 2009-04-10 | 2014-01-29 | 沙特基础工业公司 | Process for the production of an ethylene polymer using a chromium containing catalyst |
| US9586872B2 (en) | 2011-12-30 | 2017-03-07 | Chevron Phillips Chemical Company Lp | Olefin oligomerization methods |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0067607A2 (en) | 1982-12-22 |
| DE3275189D1 (en) | 1987-02-26 |
| EP0067607B1 (en) | 1987-01-21 |
| EP0067607A3 (en) | 1983-09-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4451573A (en) | Catalyst for polymerization of olefins | |
| US4431568A (en) | Catalyst for polymerization of olefins and polymerization process employing such catalyst | |
| US4159965A (en) | Catalyst useful for polymerizing olefins | |
| RU2165435C2 (en) | Catalyst composition used for polymerization of olefins | |
| CA1141368A (en) | Olefine polymerisation catalyst and the production and use thereof | |
| US4148754A (en) | Process for the preparation of a catalyst and catalyst used in olefin polymerization | |
| US4109071A (en) | Process for the polymerization of olefins | |
| EP0060443B1 (en) | Catalyst and use of same for polymerization | |
| US4027089A (en) | Process for polymerizing ethylene | |
| HU204291B (en) | Process for producing polymerizing catalyst component on carrier and polymerizing process | |
| HUT72714A (en) | Metallocene catalyst system, preparation thereof and polimerization process | |
| EP0808841A2 (en) | Supported metallocene complex and process for its preparation | |
| CA1159040A (en) | Production of catalyst component, catalyst, and use thereof | |
| US4454242A (en) | Catalyst for polymerization of olefins | |
| US5334568A (en) | Catalytic solid for use in the polymerization of alpha-olefines, process for preparing it and process for the polymerization of alpha-olefines in the presence of a catalyst system containing this solid | |
| US4203867A (en) | Transition metal composition and production thereof | |
| US4381252A (en) | Catalyst for producing polyolefins | |
| US4407727A (en) | Method of supporting a catalyst on polyolefins | |
| US4452912A (en) | Process for producing a supported catalyst for the polymerization of .alpha. | |
| US3876554A (en) | Organotin chromate polymerization catalyst | |
| US4387045A (en) | Olefin polymerization catalyst and a process for producing polyolefins by the use of said catalyst | |
| US3941761A (en) | Method of polymerizing olefins | |
| JPS601325B2 (en) | Polymerization method of vinyl halide and/or vinylidene halide | |
| JPS64969B2 (en) | ||
| JPH0216761B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: ASAHI KASEI KOGYO KABUSHIKI KAISHA 2-6, DOJIMAHAMA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:IKEGAMI, TADASHI;TAKAYA, KATSUHIKO;YONEDA, HARUYUKI;REEL/FRAME:004006/0884 Effective date: 19820510 Owner name: ASAHI KASEI KOGYO KABUSHIKI KAISHA 2-6, DOJIMAHAMA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:IKEGAMI, TADASHI;TAKAYA, KATSUHIKO;YONEDA, HARUYUKI;REEL/FRAME:004006/0884 Effective date: 19820510 |
|
| STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
| FEPP | Fee payment procedure |
Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
| FPAY | Fee payment |
Year of fee payment: 4 |
|
| FEPP | Fee payment procedure |
Free format text: PAYER NUMBER DE-ASSIGNED (ORIGINAL EVENT CODE: RMPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
| FPAY | Fee payment |
Year of fee payment: 8 |
|
| FPAY | Fee payment |
Year of fee payment: 12 |